CT BR2618-2 Si

Supporting Information
Alkyl-GeMe3: Neutral Metalloid Radical Precursors upon Visible-

Light Photocatalysis
Q.-H. Xu, L.-P. Wei, B. Xiao*
Supporting Information
List of Content
1. General information .......................................................................................................2

1.1 Reagent information .................................................................................................................2
1.2 Analytical information .............................................................................................................2
2. Reaction condition optimization ...................................................................................3
3. Compounds preparation and characterization ..............................................................5
3.1 Preparation and characterization of alkyltrimethylgermane ..................................................5
3.2 General procedure of radical addition reaction and characterization of the products ........12
3.3 General procedure of Ni catalyzed photoredox cross-coupling reaction and characterization
of the products............................................................................................................................... 22
4. Mechanism studies .......................................................................................................31
4.1 Preparation of 5. ..................................................................................................................... 31
4.2 Competitive radical addition using 5 .................................................................................... 32
4.3 Cyclic voltammogram ............................................................................................................36
4.4 Stern-Volmer Fluorescence Quenching Studies ...................................................................36
5 Crystal structure determination of 1n and 1o ..............................................................37
5.1 Experimental procedure and crystal data of 1n. ...................................................................37
5.2 Experimental procedure and crystal data of 1o. ...................................................................47
6 Reference .......................................................................................................................55
7 NMR spectra ..................................................................................................................56
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1. General information
1.1 Reagent information
All reagents were purchased from commercial source and used without further purification unless
otherwise noted. Anhydrous CH3CN, dichloroethane and MeOH was purchased from J&K Scientific Ltd.,
3,6-di-tert-butyl-9-mesityl-10-methylacridin-10-ium tetrafluoroborate was purchased from Bide
Pharmatech Ltd. Methylmagnesium bromide and other Grignard Reagents solution were purchased from
Energy Chemical, Ni(phen)Cl2[1], GeCl2•dioxane [2], trimethylgermanium bromide[3] were synthesized
according to reported literatures. Silica gel (300-400 mesh, pH = 6-7, HG/T2354-2010) was purchased
from Branch Qingdao Haiyang Chemical Co., Ltd.. Other reagents and solvents were used as received
unless otherwise noted.
1.2 Analytical information
1
H-NMR spectra were recorded on 400 MHz spectrometers. Chemical shifts of 1H-NMR spectra were
reported in parts per million relative to tetramethylsilane (δ = 0). Data for 1 H-NMR were reported as
follows: chemical shift (δ ppm), multiplicity, coupling constant (Hz), and integration. 13C-NMR spectra
were recorded on 101 MHz spectrometers. Chemical shifts were reported in parts per million relative to
the solvent resonance as the internal standard (CDCl 3, δ 77.2 ppm). Data for 13C-NMR are reported in
terms of chemical shift (δ ppm), multiplicity, and coupling constant (Hz). High-resolution mass spectra
(HRMS) were recorded on an Acquity UPLC-Xevo G2 QTof instrument with ESI mode or Thermo
Scientific Q Exactive GC Mass Spectrometer with EI mode unless otherwise stated. IR spectrum was
recorded on a Bruker Tensor 27 FT-IR Spectrometer. Gas chromatographic (GC) analysis was acquired
on a Shimadzu GC-2014 Series GC system equipped with a flame-ionization detector. GC-MS analysis
was acquired on a Shimadzu GCMS-QP2010 SE system. Cyclic voltammogram was recorded on a
chi760e electrochemical workstation. Organic solutions were concentrated under reduced pressure on a
Buchi rotary evaporator. Chromatographic purification of products was accomplished using column
chromatography on silica gel. Irradiation of the reactions was accomplish using a Roger tech Ltd. RLH-
18 photoreactor equipped with 10 W 460 nm LED.
Figure S1. Photocatalytic reaction set-up.
S2
2. Reaction condition optimization
To an oven-dried 10 mL screw-capped tube equipped with stir bar was charge with 7.7 mg (0.05 mmol)
benzalmalononitrile and 3%mol photocatalyst. The tube was vacuumed and backfilled with argon for
three cycles. 0.2 mL solvent was added followed by addition of 12.0 mg (0.06 mmol)
cyclohexyltrimethylgermane. The tube was sealed with a Teflon stopper and irradiated using a 5 W 460
nm LED lamp for 24 hours. 9.1 mg (0.05 mmol) benzophenone was added as internal standard, followed
by extracted with ethyl acetate and water. Yield was then determined by GC analysis.
Table S1. Screening of the photocatalysts.
S3
Table S2. Screening of the solvents and other conditions. [a]: Reaction carried in dark; [b]: Reaction
carried in air.
S4
3. Compounds preparation and characterization
3.1 Preparation and characterization of alkyltrimethylgermane
General Procedure A:
Magnesium powder (24 mmol, 4.0 eq.) was placed into a Schlenk tube equipped with a stir bar. the
tube was vacuumed and backfilled with argon for three cycles. The powder was activated by adding
hydrochloric acid (~ 1 M solution in EtOH) and then washed with EtOH and anhydrous THF sequentially.
To the activated Mg powder was added 20 mL anhydrous THF. Then the suspension was allowed to
warm to 40 ℃ and alkyl bromide (12 mmol, 2.0 eq.) was added in an-hour period. The mixture was
stirred for another 12 h until no alkyl bromide left (monitored by TLC). After standing by and cooling to
room temperature, the clear Grignard reagent solution was transport into another Schlenk tube filled with
argon via syringe. Trimethylgermanium bromide (6 mmol, 1.0 eq.) was added dropwise, the mixture was
then stirred at 40 ℃ for 16 h before quenched with saturated NH4Cl solution. The mixture was extracted
with ethyl ether (30 mL x 3 ). Combined organic layer was washed with brine, dried over Na2SO4 and
concentrated to less than 10 mL under reduced pressure carefully. Purification was accomplished by
distillation or flash column chromatography.
General Procedure B:
GeCl2•dioxane ( 10 mmol ) was added into a Schlenk tube equipped with a stir bar. Alkyl bromide
(1.1 eq. for 3°alkyl or benzyl, 2 eq. for 1°alkyl) was added and the tube was sealed and heated until
GeCl2•dioxane fully converted (120 ℃, 18 h for 3°alkyl or benzyl, 130 ℃, 36 h for 1°alkyl ). 1,4-
dioxane and alkyl bromide were removed under reduced pressure. The residue was dissolved into 10 mL
anhydrous diethyl ether and added to MeMgBr solution (45 mL, 1.0 M in diethyl ether) slowly. The
resulting mixture was allowed to stirred at room temperature for 12 hours before quenched with saturated
NH4Cl solution. The mixture was extracted with ethyl ether (30 mL x 3 ), washed with brine, dried over
Na2SO4 and concentrated to less than 10 mL under reduced pressure carefully. Purification was
accomplished by distillation or flash column chromatography.
Cyclotrimethylgermane (1a)
According to General Procedure A, 1.288 mL (10 mmol) Me3GeBr and 20 mmol cyclohexylmagnesium
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chloride (2 M in Et2O) was used. The crude product was distilled (3.0 kPa, 76 ℃) to give 1.48 g colorless
liquid, 74% yield.
1
H NMR (400 MHz, CDCl3) δ 1.79 – 1.48 (m, 5H), 1.29 – 0.98 (m, 5H), 0.82 (tt, J = 12.2, 3.1 Hz,
1H), 0.09 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 28.62, 28.20, 27.72, 26.96, -4.51.
IR v = 2919, 2849, 1446, 1234, 820, 596 cm-1.
HRMS (EI) m/z (M+•) Calcd for C9H20 Ge: 202.07768; Found: 202.07696.
Trimethyl(pentan-3-yl)germane (1b)
According to General Procedure A, 772.8 μL (6 mmol) Me3 GeBr and 1.49 mL (12 mmol) 3-
bromopentane was used. The crude product was distilled (4.5 kPa, 46 ℃) to give 424.3 mg colorless
liquid, 37% yield.
1
H NMR (400 MHz, CDCl3) δ 1.55 – 1.40 (m, 4H), 0.88 (t, J = 7.4 Hz, 6H), 0.87 – 0.77 (m, 1H), 0.10
(s, 9H).
13
C NMR (101 MHz, CDCl3) δ 28.33, 19.55, 9.80, -5.88.
IR v = 2963, 2933, 2909, 2876, 2860, 1459, 1235, 821, 594 cm-1.
Cyclopentyltrimethylgermane (1c)
According to General Procedure A, 0.773 mL (6 mmol) Me3 GeBr and 12 mL cyclopentylmagnesium
bromide (1 M in THF) was used. The crude product was distilled (3.4 kPa, 56 ℃) to give 633.2 mg
colorless liquid, 56% yield.
1
H NMR (400 MHz, CDCl3) δ 1.77 (m, 2H), 1.60 – 1.47 (m, 4H), 1.32 – 1.19 (m, 2H), 1.08 (tt, J =
10.3, 8.0 Hz, 1H), 0.07 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 28.75, 27.27, 26.60, -3.76.
IR v = 2950, 2909, 2865, 1450, 1235, 820, 597 cm-1.
Bicyclo[4.2.0]octa-1,3,5-trien-7-yltrimethylgermane (1d)
According to General Procedure A, 0.387 mL (3 mmol) Me3 GeBr and 1.098 g (6 mmol) 1-
bromobenzocyclobutene was used. The crude product was purified by flash column chromatography
(hexane) to give 619.7 mg colorless oil, 93% yield.
1
H NMR (400 MHz, CDCl3) δ 7.19 – 7.03 (m, 2H), 7.00 (d, J = 7.0 Hz, 1H), 6.95 – 6.89 (m, 1H), 3.31
(dd, J = 14.1, 5.7 Hz, 1H), 3.21 – 3.11 (m, 1H), 2.94 (dd, J = 14.2, 2.6 Hz, 1H), 0.12 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 149.44, 144.34, 126.69, 125.35, 122.55, 122.23, 121.04, 33.34, 32.02,
-3.67.
IR v = 3065, 2971, 2913, 1458, 1236, 1189, 999, 944, 822, 738, 705, 600, 564 cm-1.
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(Adamantan-1-yl)trimethylgermane (1e)
According to General Procedure B, 930.4 mg (4 mmol) GeCl2•dioxane and 946.6 mg (4.4 mmol) 1-
bromoadamantane was used. The crude product was purified by flash column chromatography (hexane)
to give 473.8 mg white solid, 47% yield.
1
H NMR (400 MHz, CDCl3) δ 1.86 (m, 3H), 1.76 (m, 6H), 1.70 (m, 6H), -0.01 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 38.60, 37.65, 28.35, -6.60.
IR v = 2967, 2893, 2844, 2849, 1448, 1341, 1261, 1231, 1097, 819, 743, 595, 569 cm-1.
HRMS (EI) m/z (M+•) Calcd for C13H24 Ge: 254.10898; Found: 254.10849
(3,5-dimethyladamantan-1-yl)trimethylgermane (1f)
According to General Procedure B, 930.4 mg (4 mmol) GeCl2•dioxane and 1.070 g (4.4 mmol) 1-bromo-
3,5-dimethyladamantane was used. The crude product was purified by flash column chromatography
(hexane) to give 1.0183 g colorless oil, 91% yield.
1
H NMR (400 MHz, CDCl3) δ 1.97 (h, J = 3.2 Hz, 1H), 1.57 – 1.20 (m, 10H), 1.19 – 1.07 (m, 2H),
0.77 (s, 6H), 0.00 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 51.54, 44.91, 43.73, 37.05, 31.06, 30.38, 29.52, 26.15, -6.44.
IR v = 2943, 2895, 2836, 1454, 1373, 1356, 1341, 1235, 1151, 984, 951, 819, 748, 595, 566 cm-1.
Trimethyl(tert-pentyl)germane (1g)
According to General Procedure B, 1.698 g (7.3 mmol) GeCl2•dioxane and 1.01 mL (8.0 mmol) 2-
bromo-2-methylbutane was used. The crude product was distilled (1 atm, 124℃) to give 912.4 mg low-
melting solid; 66% yield.
1
H NMR (400 MHz, CDCl3) δ 1.35 (q, J = 7.5 Hz, 2H), 0.91 (s, 6H), 0.83 (t, J = 7.5 Hz, 3H), 0.06 (s,
9H).
13
C NMR (101 MHz, CDCl3) δ 33.03, 24.01, 23.88, 9.12, -4.35.
IR v = 2966, 2940, 2917, 2882, 2857, 1460, 1408, 1381, 1364, 1234, 819, 782, 746, 593, 573 cm-1.
Trimethyl(1-methylcyclohexyl)germane (1h)
1-Bromo-1-methylcyclohexane was prepared as reported[4]. According to General Procedure B, 930.4
mg (4 mmol) GeCl2•dioxane and 0.621 mL (4.4 mmol) 1-bromo-1-methylcyclohexane was used. The
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crude product was purified by flash column chromatography (hexane) to give 439.5 mg colorless liquid,
51% yield.
1
H NMR (400 MHz, CDCl3) δ 1.61 – 1.44 (m, 5H), 1.43 – 1.20 (m, 5H), 1.00 (s, 3H), 0.04 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 34.09, 26.83, 24.42, 21.41, 20.56, -5.10.
IR v = 2970, 2923, 2859, 1446, 1233, 819, 791, 745, 594 cm-1.
(1-butylcyclohexyl)trimethylgermane (1i)
1-Bromo-1-butylcyclohexane was prepared as reported[5]. According to General Procedure B, 465.2 mg
(2 mmol) GeCl2•dioxane and 482.2 mg (2.2 mmol) 1-bromo-1-butyl-cyclohexane was used. The crude
product was purified by flash column chromatography (hexane) to give 441.6 mg colorless oil, 86% yield.
1
H NMR (400 MHz, CDCl3) δ 1.53 – 1.35 (m, 10H), 1.31 – 1.25 (m, 2H), 1.24 – 1.17 (m, 2H), 1.16 –
1.08 (m, 2H), 0.84 (t, J = 7.2 Hz, 3H), 0.07 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 35.26, 33.33, 29.90, 28.87, 27.70, 24.82, 22.19, 15.15, -2.19.
IR v = 2957, 2927, 2859, 1451, 1233, 856, 821, 748, 591 cm-1.
Benzyltrimethylgermane (1j)
According to General Procedure B, 6.98 g (30 mmol) GeCl2•dioxane and 3.57 mL (31 mmol) benzyl
chloride was used. The crude product was distilled (2.0 kPa, 79℃) to give 4.682 g colorless liquid, 75%
yield.
1
H NMR (400 MHz, CDCl3) δ 7.20 (tt, J = 8.3, 1.8 Hz, 2H), 7.05 (td, J = 7.2, 1.3 Hz, 1H), 7.01 – 6.97
(m, 2H), 2.20 (s, 2H), 0.10 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 141.42, 128.15, 127.61, 123.78, 26.32, -2.53.
IR v = 3061, 3025, 2972, 2907, 1600, 1493, 1452, 1236, 1207, 1142, 1055, 1030, 824, 766, 698, 600,
566, 460 cm-1.
Trimethyl(phenethyl)germane (1k)
According to General Procedure B, 465.2 mg (2 mmol) GeCl2•dioxane and 0.546 mL (4 mmol) (2-
bromoethyl)benzene was used. The crude product was purified by flash column chromatography (hexane)
to give 276.7 mg colorless liquid, 62% yield.
1
H NMR (400 MHz, CDCl3) δ 7.26 – 7.09 (m, 5H), 2.70 – 2.54 (m, 2H), 1.10 – 0.93 (m, 2H), 0.07 (s,
9H).
13
C NMR (101 MHz, CDCl3) δ 149.07, 132.32, 131.89, 129.56, 35.20, 22.61, 1.62.
IR v = 3085, 3063, 3027, 2970, 2930, 2906, 2851, 1603, 1494, 1454, 1236, 824, 751, 699, 598 cm-1.
HRMS (EI) m/z ([M-CH3]+) Calcd for C10 H15 Ge: 209.03855; Found: 209.03787.
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Trimethyl(3-phenylpropyl)germane (1l)
According to General Procedure B, 465.2 mg (2 mmol) GeCl2•dioxane was used. The crude product was
purified by flash column chromatography (hexane) to give 276.7 mg colorless liquid, 62% yield.
1
H NMR (400 MHz, CDCl3) δ 7.31 – 7.25 (m, 2H), 7.21 – 7.14 (m, 3H), 2.61 (t, J = 7.7 Hz, 2H), 1.73
– 1.59 (m, 2H), 0.78 – 0.67 (m, 2H), 0.10 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 142.69, 128.47, 128.22, 125.61, 39.67, 27.29, 16.67, -2.36.
IR v = 3086, 3063, 3027, 2970, 2927, 2856, 1604, 1496, 1454, 1236, 822, 745, 698, 598 cm-1.
HRMS (EI) m/z ([M-CH3]+) Calcd for C11 H17 Ge: 223.05420; Found: 223.05310.
3-methyl-3-(trimethylgermyl)butanoic acid (1m)

To a 250 mL Schlenk flask was charged with 12.56 g (120 mmol) GeO2. The flask was then vacuumed
and backfilled with argon for three times. 48 mL (30%) concentrated hydrochloric acid and 26.4 mL
(35%) hypophosphorous acid. The mixture was stirred at 80 oC for 4 hours before cooled to room
temperature. Another 48 mL (35%) concentrated hydrochloric acid was added, followed by 11.514g (115
mmol) 3,3-dimethylacrylic acid. The mixture was stirred at room temperature for 12 hours. Resulting
white precipitate was filtered and washed with concentrated hydrochloric acid, dried under vacuum and
then transferred to an oven dried Schlenk flask. After vacuumed and backfilled with argon for three times,
the flask was cooled to 0 oC. 130 mL anhydrous diethyl ether was added. 465 mmol MeMgBr (3 M in
Et2O) was added in a 20-minutes period. The mixture was warmed to reflux for 40 minutes, and then
poured into excess diluted hydrochloric acid (2 M). The mixture was extracted with diethyl ether (100
mL x 3), combined organic layers was dried over Na2SO4, concentrated under reduced pressure to give
20.545 g title product as a pale yellow thick oil. NMR spectrum suggested that the product was almost
pure.
1
H NMR (400 MHz, CDCl3) δ 2.28 (s, 2H), 1.09 (s, 6H), 0.11 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 179.19, 44.05, 24.12, 22.43, -4.80.
IR v = 2963, 2919, 2861, 1706, 1463, 1439, 1409, 1312, 1234, 1108, 947, 822, 752, 596 cm-1.
HRMS (ESI) m/z ([M+Na]+) Calcd for C8H18 GeNaO2: 243.0411; Found: 243.0410.
3-methyl-3-(trimethylgermyl)butanoic acid diosgenin ester (1n)

To a screw-capped flask was charged with 61.1 mg (0.5 mmol) 4-dimethylaminopyridine , 414.6 mg
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(1.0 mmol) diosgenin and 287.6 mg (1.5 mmol) 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide
hydrochloride. After vacuumed and backfilled with argon for three times, 10 mL DCM and 262.6 mg
(1.2 mmol) 3-methyl-3-(trimethylgermyl)butanoic acid was added. The mixture was allowed to stirred
at room temperature for 12 hours. Deionized water was then added and the mixture was extracted with
DCM (25 mL x 3). Combined organic layers was dried over Na2SO4 and concentrated under vacuum to
give the crude product, which was purified by flash colume chromatography (petroleum ether/ethyl
acetate 20/1) to give 517.7 mg title product as a white powder. 86% yield.
1
H NMR (400 MHz, CDCl3) δ 5.42 – 5.34 (m, 1H), 4.69 – 4.52 (m, 1H), 4.41 (ddd, J = 8.6, 7.6, 6.4
Hz, 1H), 3.47 (ddd, J = 11.0, 4.4, 2.1 Hz, 1H), 3.37 (t, J = 10.9 Hz, 1H), 2.33 (d, J = 8.1 Hz, 2H), 2.22
(s, 2H), 2.08 – 1.92 (m, 2H), 1.90 – 1.82 (m, 3H), 1.78 (dd, J = 8.6, 6.7 Hz, 1H), 1.75 – 1.70 (m, 1H),
1.67 (t, J = 5.0 Hz, 1H), 1.65 – 1.56 (m, 6H), 1.55 – 1.39 (m, 3H), 1.29 (ddd, J = 13.7, 11.8, 6.4 Hz,
1H), 1.20 (dd, J = 12.5, 4.9 Hz, 1H), 1.12 (ddd, J = 13.5, 8.8, 4.2 Hz, 2H), 1.06 (s, 6H), 1.04 (s, 3H),
0.97 (d, J = 6.9 Hz, 3H), 0.80 – 0.77 (m, 6H), 0.10 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 171.91, 139.78, 122.30, 109.28, 80.82, 73.59, 66.85, 62.09, 56.44,
49.96, 44.36, 41.62, 40.26, 39.74, 38.32, 37.00, 36.76, 32.05, 31.85, 31.41, 30.31, 28.82, 27.98, 24.09,
24.07, 22.55, 20.82, 19.36, 17.14, 16.29, 14.53, -4.81.
IR v = 2943, 2909, 2881, 2861, 2850, 2832, 1733, 1457, 1378, 1342, 1246, 1193, 1128, 1081, 1071,
1062, 1050, 1032, 1009, 980, 963, 919, 899, 865, 819, 750, 596, 572 cm-1.
HRMS (ESI) m/z ([M+H]+) Calcd for C35H59 GeO4: 617.3625; Found: 617.3629.
3-Methyl-3-(trimethylgermyl)butan-1-ol (1o)
To a screw-capped tube vacuumed and backfilled with argon was charged with 49.3 mg (1.3 mmol)
LiAlH4 and 0.6 mL anhydrous diethyl ether. The mixture was cooled to 0 oC and 218.9 g (1 mmol) 3-
methyl-3-(trimethylgermyl)butanoic acid in 1.6 mL diethyl ether was added carefully. The mixture was
warmed to 35 oC and stirred for 5 hours, the reaction was quenched by adding excess NaOH solution ,
extracted with diethyl ether (40 mL x 3) and concentrated under reduced pressure carefully to give the
crude product as a yellow thick oil, which was purified by flash column chromatography (petroleum
ether/ethyl acetate 30/1) to give 186.5 mg colorless low-melted solid, 91% yield.
1
H NMR (400 MHz, CDCl3) δ 3.75 – 3.64 (m, 2H), 1.75 – 1.55 (m, 3H), 0.98 (s, 6H), 0.08 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 58.97, 42.31, 23.52, 21.10, -5.61.
IR v = 3332, 2956, 2922, 2886, 2857, 1462, 1410, 1384, 1364, 1060, 1034, 1018, 990, 965, 821, 748,
595 cm-1.
HRMS (ESI) m/z ([M+Na]+) Calcd for C8H20 GeNaO: 229.0618; Found: 229.0633.
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Trimethyl(2-methyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propan-2-yl)germane (1p)
To a 100 mL round-bottom flask was charged with 2.2696 g (11 mmol) dicyclohexylcarbodiimide,
122.2 mg (1 mmol) 4-dimethylaminopyridine and 1.794 g (11 mmol) N-hydroxyphthalimide. 50 mL
dichloromethane and 2.189 g (10 mmol) 3-methyl-3-(trimethylgermyl)butanoic acid was added in
sequence. The mixture was stirred at room temperature while monitored by TLC. After almost all starting
material consumed, the mixture was filtered and concentrated under vacuum to give crude NHP ester as
an off-white powder. Purification by recrystallization from methanol give 3.22 g 1,3-dioxoisoindolin-2-
yl 3-methyl-3-(trimethylgermyl)butanoate as a white powder.
1
H NMR (400 MHz, CDCl3) δ 7.94 – 7.84 (m, 2H), 7.79 (dd, J = 5.5, 3.1 Hz, 2H), 2.60 (s, 2H), 1.20
(s, 6H), 0.15 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 168.11, 162.08, 134.73, 128.97, 123.96, 40.59, 23.45, 22.55, -4.97.
IR v = 2969, 2950, 2926, 2863, 1806, 1783, 1746, 1467, 1436, 1371, 1356, 1271, 1237, 1184, 1155,
1140, 1081, 1060, 972, 958, 912, 879, 827, 785, 752, 713, 695, 655, 602, 582, 519, 502 cm-1.
HRMS (ESI) m/z ([M+H]+) Calcd for C16H22 GeNO4: 366.0761; Found: 366.0762.
According to the procedure reported by Baran et al[6], to a 25 mL screw-capped tube was added 1.524
g (6 mmol) bis(pinacolato)diboron, 728.0 mg (2.0 mmol) 1,3-dioxoisoindolin-2-yl 3-methyl-3-
(trimethylgermyl)butanoate, 157.1 mg (0.6 mmol) Cu(acac)2, 1.26 g finely grinded LiOH•H2 O and 285.7
mg MgCl2. The tube was vacuumed and backfilled with argon for three times. 14 mL mixture of 1,4-
dioxane and DMF (4:1) was added. The mixture was stirred at room temperature for 10 minutes until the
color turned to dark brown. Excess saturated NH4Cl solution and EtOAc was added. The mixture was
extracted with EtOAc (2 mL x 3). Combined organic layer was dried over Na2SO4, and concentrated
under vacuum. Purification by flash column chromatography give 301.7 mg title product as a colorless
oil, 46% yield overall.
1
H NMR (400 MHz, CDCl3) δ 1.25 (s, 12H), 1.03 (s, 6H), 0.84 (s, 2H), 0.04 (s, 9H).
13
C NMR (101 MHz, CDCl3) δ 82.83, 26.08, 24.99, 24.96, 21.35, -5.09.
IR v = 2979, 2949, 2939, 2914, 2857, 1461, 1409, 1371, 1347, 1321, 1274, 1231, 1147, 1110, 974,
888, 849, 819, 746, 593 cm-1.
HRMS (EI) m/z ([M-CH3]+) Calcd for C12 H16BGeO2: 287.12376; Found: 287.12290.
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4-methyl-2-(2-methyl-2-(trimethylgermyl)propyl)quinolone (1q)
Reaction was carried as the literature reported[7]: To an oven-dried 10 mL screw-capped tube equipped
with stir bar was charged with 430.0 mg (1 mmol) (bis(trifluoroacetoxy)iodo)benzene. After vacuumed
and backfilled with argon for three cycles, 4 mL anhydrous MeCN, 437.7 mg (2 mmol) 3-methyl-3-
(trimethylgermyl)butanoic acid and 52.9 μL (0.4 mmol) lepidine was added. The mixture was irradiated
with an 8 W 460 nm LED lamp (1 cm) for 48 hours. Saturated NaHCO3 solution was then added.
Resulting mixture was extracted with ethyl acetate (20 mL x 3) and washed with saturated NaHCO3
solution, water and brine. Organic layer was separated, dried over Na2SO4, concentrated under reduced
pressure to give crude product, which was purified by flash column chromatography (petroleum
ether/ethyl acetate 30/1) to give 54.2 mg title compound as a thick oil, 43% yield.
1
H NMR (400 MHz, CDCl3) δ 8.08 (d, J = 8.4 Hz, 1H), 7.96 (dd, J = 8.3, 1.4 Hz, 1H), 7.67 (ddd, J =
8.3, 6.7, 1.4 Hz, 1H), 7.54 – 7.48 (m, 1H), 7.08 (s, 1H), 2.93 (s, 2H), 2.68 (s, 3H), 1.03 (s, 6H), 0.09 (s,
9H).
13
C NMR (101 MHz, CDCl3) δ 160.16, 129.46, 128.93, 126.67, 125.46, 124.21, 123.60, 48.08, 25.19,
24.00, 18.78, -4.61.
IR v = 3063, 3034, 2957, 2936, 2914, 2854, 1603, 1560, 1509, 1463, 1449, 1411, 1383, 1364, 1353,
1233, 1188, 1025, 821, 755, 594, 572 cm-1.
HRMS (ESI) m/z ([M+H]+) Calcd for C17H26 GeN2: 318.1277; Found: 318.1287.
3.2 General procedure of radical addition reaction and characterization of the products
Radical acceptors were purchased from commecial source unless otherwise noted.
General Procedure C:
To an oven-dried 10 mL screw-capped tube equipped with stir bar was charge with 0.2 mmol radical
acceptor and 3.1 mg (3% mmol) 3,6-di-tert-butyl-9-mesityl-10-methylacridin-10-ium tetrafluoroborate.
The tube was vacuumed and backfilled with argon for three cycles. 0.4 mL anhydrous MeCN and 0.4
mL MeOH was added followed by addition of 0.24 mmol alkyltrimethylgermane. The tube was sealed
with a Teflon stopper and irradiated using an 8 W 460 nm LED lamp for 24 hours. The reaction mixture
was then extracted with ethyl acetate and water. Organic layer was separated, dried over Na2SO4, and
concentrated under reduced pressure. The product was purified by flash column chromatography.
2-(cyclohexyl(phenyl)methyl)malnonitrile (3a)
According to General Procedure C, 48.2 mg cyclotrimethylgermane and 30.8 mg benzalmalononitrile
were used. The crude product was purified by flash column chromatography (petroleum ether/ethyl
acetate 5/1) to give 46.9 mg title product as a pale yellow syrup, 98% yield.
1
H NMR (400 MHz, CDCl3) δ 7.44 – 7.36 (m, 3H), 7.34 – 7.29 (m, 2H), 4.19 (d, J = 5.5 Hz, 1H), 2.88
(dd, J = 9.8, 5.5 Hz, 1H), 2.07 – 1.96 (m, 1H), 1.93 (dt, J = 12.1, 3.2 Hz, 1H), 1.85 (dtd, J = 13.1, 3.6,
1.8 Hz, 1H), 1.65 (ddt, J = 12.0, 4.4, 2.3 Hz, 2H), 1.52 – 1.41 (m, 1H), 1.43 – 1.33 (m, 1H), 1.29 – 1.19
(m, 1H), 1.19 – 1.12 (m, 1H), 1.12 – 1.01 (m, 1H), 0.88 – 0.75 (m, 2H).
S12
13
C NMR (101 MHz, CDCl3) δ 136.69, 129.12, 128.73, 128.30, 112.20, 111.93, 52.34, 39.22, 31.19,
30.58, 27.11, 25.84, 25.81, 25.72.
HRMS (ESI) m/z ([M+H]+) Calcd for C16H18N2: 239.1548; Found: 239.1540.
2-(2-ethyl-1-phenylbutyl)malononitrile (3b)
According to General Procedure C, 45.3 mg trimethyl(pentan-3-yl)germane and 30.8 mg
benzalmalononitrile were used. The crude product was purified by flash column chromatography
(petroleum ether/ethyl acetate 5/1) to give 32.0 mg title product as a pale yellow syrup, 71% yield.
1
H NMR (400 MHz, CDCl3) δ 7.44 – 7.31 (m, 5H), 4.15 (d, J = 5.6 Hz, 1H), 3.09 (dd, J = 10.1, 5.6
Hz, 1H), 2.14 – 2.01 (m, 1H), 1.59 (dqd, J = 14.8, 7.5, 4.9 Hz, 2H), 1.47 (dp, J = 14.4, 7.2 Hz, 1H),
1.34 (dqd, J = 14.9, 7.5, 3.4 Hz, 1H), 1.09 (dp, J = 14.8, 7.5 Hz, 1H), 0.98 (t, J = 7.5 Hz, 3H), 0.78 (t, J
= 7.4 Hz, 3H).
13
C NMR (101 MHz, CDCl3) δ 136.63, 129.14, 128.77, 128.37, 112.21, 111.94, 48.73, 41.09, 27.70,
21.53, 21.46, 9.92, 9.65.
2-(cyclopentyl(phenyl)methyl)malononitrile (3c)
According to General Procedure C, 44.8 mg cyclopentyltrimethylgermane and 30.8 mg
(petroleum ether/ethyl acetate 5/1) to give 32.6 mg title product as a pale orange syrup, 73% yield.
1
H NMR (400 MHz, CDCl3) δ 7.44 – 7.31 (m, 5H), 4.08 (d, J = 4.5 Hz, 1H), 2.92 (dd, J = 11.0, 4.5
Hz, 1H), 2.55 (dtd, J = 16.7, 10.0, 6.7 Hz, 1H), 2.05 (dtd, J = 11.1, 7.3, 3.5 Hz, 1H), 1.83 – 1.52 (m,
5H), 1.28 (dq, J = 11.7, 9.1 Hz, 1H), 1.12 – 0.98 (m, 1H).
13
C NMR (101 MHz, CDCl3) δ 137.34, 129.08, 128.77, 128.20, 112.09, 111.83, 52.28, 42.39, 31.68,
31.63, 29.18, 25.48, 24.76.
HRMS (EI) m/z (M+•) Calcd for C15H16N2: 224.13135; Found: 224.13061
2-(bicyclo[4.2.0]octa-1,3,5-trien-7-yl(phenyl)methyl)malononitrile (3d)
According to General Procedure C, 53.0 mg bicyclo[4.2.0]octa-1,3,5-trien-7-yltrimethylgermane and
30.8 mg benzalmalononitrile were used. The crude product was purified by flash column chromatography
(petroleum ether/ethyl acetate 8/1) to give 51.4 mg title product as a pale yellow syrup, 99% yield, 1:1
d.r.. Diastereomers can be separated by further column chromatography (petroleum ether/ethyl acetate
15/1) and the configuration was determined according to the literature[8].
S13
1
H NMR (400 MHz, CDCl3) (pref) δ 7.50 – 7.42 (m, 5H), 7.33 – 7.21 (m, 3H), 7.16 – 7.09 (m, 1H),
4.33 (d, J = 4.5 Hz, 1H), 4.18 (ddd, J = 11.6, 5.3, 2.3 Hz, 1H), 3.39 – 3.25 (m, 2H), 2.72 (dd, J = 14.6,
2.4 Hz, 1H).
13
C NMR (101 MHz, CDCl3) (pref) δ 144.75, 143.31, 135.72, 129.34, 129.25, 128.82, 128.08, 127.47,
123.75, 122.17, 111.72, 111.57, 50.62, 44.50, 35.53, 28.97.
1
H NMR (400 MHz, CDCl3) (parf) δ 7.51 – 7.36 (m, 5H), 7.20 (t, J = 7.5 Hz, 1H), 7.09 (d, J = 7.4 Hz,
1H), 7.00 (t, J = 7.6 Hz, 1H), 6.18 (d, J = 7.4 Hz, 1H), 4.19 (ddd, J = 11.4, 5.1, 2.4 Hz, 1H), 4.09 (d, J
= 5.8 Hz, 1H), 3.65 (dd, J = 14.2, 5.0 Hz, 1H), 3.40 (dd, J = 11.3, 5.8 Hz, 1H), 3.15 (dd, J = 14.2, 2.5
Hz, 1H).
13
C NMR (101 MHz, CDCl3) (parf) δ 144.75, 142.49, 136.44, 129.24, 128.61, 128.36, 127.13, 123.08,
122.66, 111.75, 111.66, 50.51, 44.92, 36.32, 28.79.
HRMS (ESI) m/z ([M+Na]+) Calcd for C18H14N2Na: 281.1049; Found: 281.1015
2-((adamantan-1-yl)(phenyl)methyl)malononitrile (3e)
According to General Procedure C, 60.7 mg (adamantan-1-yl)trimethylgermane and 30.8 mg
(petroleum ether/ethyl acetate 8/1) to give 57.8 mg title product as a off-white powder, 99% yield
1
H NMR (400 MHz, CDCl3) δ 7.52 – 7.28 (m, 5H), 4.25 (d, J = 5.4 Hz, 1H), 2.80 (d, J = 5.4 Hz, 1H),
2.02 (q, J = 3.3 Hz, 3H), 1.75 – 1.48 (m, 12H).
13
C NMR (101 MHz, CDCl3) δ 135.30, 129.69, 128.62, 128.55, 58.03, 40.39, 36.55, 36.35, 28.38,
28.34, 23.77.
2-((3,5-dimethyladamantan-1-yl)(phenyl)methyl)malononitrile (3f)
According to General Procedure C, 67.4 mg (adamantan-1-yl)trimethylgermane and 30.8 mg
(petroleum ether/ethyl acetate 8/1) to give 57.8 mg title product as a yellow syrup, 99% yield.
1
2.10 (h, J = 3.3 Hz, 1H), 1.53 (d, J = 3.3 Hz, 2H), 1.35 – 1.22 (m, 8H), 1.18 – 1.02 (m, 2H), 0.82 (d, J
= 3.5 Hz, 6H).
13
C NMR (101 MHz, CDCl3) δ 135.27, 128.67, 128.58, 113.43, 113.22, 77.36, 77.04, 76.72, 57.55,
50.48, 46.72, 42.59, 42.56, 42.39, 38.88, 38.38, 31.43, 31.40, 30.50, 29.38, 23.98.
2-(2,2-dimethyl-1-phenylbutyl)malononitrile (3g)
S14
According to General Procedure C, 45.3 mg trimethyl(tert-pentyl)germane and 30.8 mg
1
H NMR (400 MHz, CDCl3) δ 7.40 (q, J = 4.5, 3.4 Hz, 5H), 4.21 (d, J = 5.4 Hz, 1H), 3.07 (d, J = 5.4
Hz, 1H), 1.39 (qd, J = 7.4, 1.9 Hz, 2H), 1.12 (s, 3H), 0.99 (s, 3H), 0.89 (t, J = 7.4 Hz, 3H).
13
C NMR (101 MHz, CDCl3) δ 136.02, 129.58, 128.72, 128.60, 113.34, 113.14, 55.08, 37.48, 33.41,
24.85, 24.75, 24.53, 8.18.
2-((1-methylcyclohexyl)(phenyl)methyl)malononitrile (3h)
According to General Procedure C, 51.6 mg trimethyl(1-methylcyclohexyl)germane and 30.8 mg
(petroleum ether/ethyl acetate 8/1) to give 49.3 mg title product as a pale brown syrup, 98% yield.
1
1.68 – 1.20 (m, 10H), 1.15 (s, 3H).
13
C NMR (101 MHz, CDCl3) δ 135.70, 129.76, 128.66, 128.57, 113.46, 113.24, 56.79, 37.32, 36.80,
36.57, 25.66, 24.25, 21.79, 21.44, 20.31.
2-((1-butylcyclohexyl)(phenyl)methyl)malononitrile (3i)
According to General Procedure C, 61.7 mg (1-butylcyclohexyl)trimethylgermane and 30.8 mg
(petroleum ether/ethyl acetate 8/1) to give 48.9 mg title product as an orange syrup, 83% yield.
1
H NMR (400 MHz, CDCl3) δ 7.47-7.32 (m, 5H), 4.19 (d, J = 5.1 Hz, 1H), 3.21 (d, J = 5.2 Hz, 1H),
1.76 – 1.38 (m, 10H), 1.37 – 1.06 (m, 6H), 0.91 (t, J = 7.0 Hz, 3H).
13
C NMR (101 MHz, CDCl3) δ 135.63, 130.00, 128.64, 128.60, 128.54, 128.50, 113.64, 113.32,
53.00, 39.75, 32.14, 32.04, 31.65, 25.44, 24.81, 24.35, 23.30, 21.34, 21.30, 14.12.
2-(1,2-diphenylethyl)malononitrile (3j)
According to General Procedure C, 50.1 mg benzyltrimethylgermane and 30.8 mg benzalmalononitrile
acetate 5/1) to give 48.6 mg title product as a pale orange syrup, 99% yield.
1
H NMR (400 MHz, CDCl3) δ 7.44 – 7.36 (m, 5H), 7.35 – 7.25 (m, 3H), 7.21 – 7.16 (m, 2H), 3.85 (d,
J = 5.1 Hz, 1H), 3.46 (ddd, J = 8.4, 7.3, 5.1 Hz, 1H), 3.32 – 3.21 (m, 2H).
S15
13
C NMR (101 MHz, CDCl3) δ 136.64, 136.43, 129.21, 129.17, 129.09, 128.93, 128.03, 127.60,
112.05, 111.43, 48.36, 38.53, 28.52.
2-(1,3-diphenylpropyl)malononitrile (3k)
According to General Procedure C, 53.5 mg trimethyl(phenethyl)germane, 30.8 mg benzalmalononitrile
and 54.1 mg K2S2O8 were used. The crude product was purified by flash column chromatography
1
H NMR (400 MHz, CDCl3) δ 7.47 – 7.38 (m, 3H), 7.35 – 7.26 (m, 4H), 7.25 – 7.19 (m, 1H), 7.08
(dd, J = 6.9, 1.7 Hz, 2H), 3.83 (d, J = 6.2 Hz, 1H), 3.17 (dt, J = 9.7, 5.8 Hz, 1H), 2.63 (ddd, J = 13.4,
8.2, 5.2 Hz, 1H), 2.45 (dt, J = 13.6, 8.1 Hz, 1H), 2.37 – 2.28 (m, 2H).
13
C NMR (101 MHz, CDCl3) δ 139.91, 136.19, 129.47, 129.12, 128.72, 128.39, 128.09, 128.06,
126.56, 111.83, 111.80, 45.56, 33.50, 32.73, 30.37.
HRMS (ESI) m/z ([M+H]+) Calcd for C17H15N2: 247.1230; Found: 247.1243
2-(1-phenylhexyl)malononitrile (3l)
According to General Procedure C, 56.8 mg trimethyl(3-phenylpropyl)germane, 30.8 mg
benzalmalononitrile and 54.1 mg K2S2O8 were used. The crude product was purified by flash column
chromatography (petroleum ether/ethyl acetate 5/1) to give 36.6 mg title product as a pale yellow syrup,
67% yield.
1
7.06 (m, 2H), 3.83 (d, J = 6.3 Hz, 1H), 3.19 (dt, J = 8.8, 6.6 Hz, 1H), 2.70 – 2.53 (m, 2H), 2.08 – 1.93
(m, 2H), 1.61 – 1.48 (m, 2H).
13
C NMR (101 MHz, CDCl3) δ 141.18, 136.47, 129.36, 128.99, 128.49, 128.32, 127.83, 126.14,
111.86, 111.83, 46.53, 35.33, 31.59, 30.31, 28.69.
5,5-dicyano-3,3-dimethyl-4-phenylpentanoic acid (3m)

According to General procedure C, to an oven-dried 10 mL screw-capped tube equipped with stir
bar was charged with 30.8 mg benzalmalononitrile and 3.1 mg (3% mmol) 3,6-di-tert-butyl-9-mesityl-
10-methylacridin-10-ium tetrafluoroborate. The tube was vacuumed and backfilled with argon for three
cycles. 0.4 mL anhydrous MeCN and 0.4 mL MeOH was added followed by addition of 52.5 mg (0.24
mmol) 5. The tube was sealed with a Teflon stopper and irradiated using a 8 W 460 nm LED lamp for 24
hours. The reaction mixture was then extracted with ethyl acetate and water. Organic layer was separated,
dried over Na2SO4, and concentrated under reduced pressure. Purification by flash column
S16
chromatography (ethyl acetate) gives 24.7 mg title product as a pale yellow syrup, 48% yield.
1
2.44 – 2.29 (m, 2H), 1.35 (s, 3H), 1.20 (s, 3H).
13
C NMR (101 MHz, CDCl3) δ 177.04, 135.21, 129.63, 129.01, 128.98, 113.32, 112.83, 52.76, 44.81,
37.11, 25.88, 25.73, 24.89.
HRMS (ESI) m/z ([M+H]+) Calcd for C15H17N2O2: 257.1290; Found: 257.1290.
2-(4-hydroxy-2,2-dimethyl-1-phenylbutyl)malononitrile (3n)
According to General procedure C, 49.2 mg (0.24 mmol) 1o and 30.8 mg benzalmalononitrile were
used. The crude product was purified by flash column chromatography (petroleum ether/ethyl acetate
1/1) to give 47.6 mg title product as a yellow syrup, 98% yield.
1
H NMR (400 MHz, CDCl3) δ 7.51 – 7.30 (m, 5H), 4.71 (d, J = 5.1 Hz, 1H), 3.82 (dt, J = 10.6, 3.9
Hz, 2H), 3.27 (d, J = 5.1 Hz, 1H), 1.83 (dt, J = 14.3, 7.0 Hz, 1H), 1.72 (s, 1H), 1.62 – 1.50 (m, 1H),
1.20 (s, 3H), 0.99 (s, 3H).
13
C NMR (101 MHz, CDCl3) δ 136.02, 129.79, 128.72, 128.60, 113.82, 113.38, 58.98, 54.74, 42.63,
37.27, 26.53, 25.40, 24.97.
HRMS (EI) m/z (M+•) Calcd for C15H18N2O: 242.14191; Found:242.14162.
2-(2,2-dimethyl-1-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl)malononitrile (3o)
According to General procedure C, 72.2 mg (0.24 mmol) 1p and 30.8 mg benzalmalononitrile were
5/1) to give 61.0 mg title product as a pale yellow syrup, 90% yield.
1
1.28 (d, J = 3.6 Hz, 12H), 1.23 (s, 3H), 1.07 (s, 3H), 1.03 – 0.91 (m, 2H).
13
C NMR (101 MHz, CDCl3) δ 136.26, 129.71, 128.61, 128.58, 128.50, 113.59, 113.30, 83.58, 56.16,
36.69, 28.59, 27.48, 24.99, 24.89.
HRMS (ESI) m/z ([M+H]+) Calcd for C20H28BN2O2: 339.2244; Found: 339.2251.
2-(2,2-dimethyl-3-(4-methylquinolin-2-yl)-1-phenylpropyl)malononitrile (3p)
According to General procedure C, 75.8 mg (0.24 mmol) 1q and 30.8 mg (0.20 mmol)
(petroleum ether/ethyl acetate 4/1) to give 69.1 mg title product as an off-white solid, 98% yield.
1
H NMR (400 MHz, CDCl3) δ 8.06 (dd, J = 8.4, 1.2 Hz, 1H), 8.01 (ddd, J = 8.3, 1.5, 0.7 Hz, 1H), 7.73
(ddd, J = 8.4, 6.9, 1.4 Hz, 1H), 7.58 (ddd, J = 8.3, 6.8, 1.3 Hz, 1H), 7.40 (d, J = 7.4 Hz, 2H), 7.35 –
S17
7.29 (m, 3H), 7.12 (t, J = 0.9 Hz, 1H), 6.74 (d, J = 4.7 Hz, 1H), 3.28 (d, J = 13.9 Hz, 1H), 3.06 (d, J =
4.8 Hz, 1H), 2.88 (d, J = 13.8 Hz, 1H), 2.73 (d, J = 0.9 Hz, 3H), 1.38 (s, 3H), 0.87 (s, 3H).
13
C NMR (101 MHz, CDCl3) δ 157.92, 147.14, 145.03, 135.94, 130.07, 129.79, 129.56, 128.49,
128.40, 128.35, 126.93, 126.39, 124.18, 123.70, 114.86, 113.58, 52.29, 49.08, 39.17, 28.27, 25.27,
25.04, 18.84.
((2-cyclohexylethyl)sulfonyl)benzene (3q)
According to General Procedure C, 48.2 mg cyclotrimethylgermane and 33.6 mg phenyl vinyl sulfone
acetate 8/1) to give 37.6 mg title product as a pale yellow thick oil, 74% yield.
1
H NMR (400 MHz, CDCl3) δ 7.91 (dd, J = 7.3, 1.7 Hz, 2H), 7.66 (t, J = 7.4 Hz, 1H), 7.58 (t, J = 7.6
Hz, 2H), 3.15 – 3.00 (m, 2H), 1.77 – 1.53 (m, 7H), 1.34 – 1.04 (m, 4H), 0.93 – 0.77 (m, 2H).
13
C NMR (101 MHz, CDCl3) δ 139.17, 133.64, 129.27, 128.05, 54.38, 36.64, 32.78, 29.61, 26.25,
26.00.
HRMS (ESI) m/z ([M+H]+) Calcd for C14H21O2S: 253.1262; Found:253.1261.
2-benzyl-3-cyclohexylpropanoic acid (3r)

According to General Procedure C, 48.2 mg cyclotrimethylgermane and 32.4 mg 2-benzyl-2-propenoic
acid were used. The crude product was purified by flash column chromatography (petroleum ether/ethyl
acetate 2/1) to give 38.0 mg title product as a yellow thick oil, 77% yield.
1
H NMR (400 MHz, CDCl3) δ 7.34 – 7.05 (m, 5H), 2.94 (dd, J = 12.6, 7.3 Hz, 1H), 2.85 – 2.64 (m,
2H), 1.82 – 1.51 (m, 6H), 1.39 – 1.02 (m, 6H), 0.95 – 0.72 (m, 2H).
13
C NMR (101 MHz, CDCl3) δ 181.65, 139.10, 128.88, 128.42, 126.41, 44.69, 39.61, 38.72, 35.50,
33.63, 32.68, 26.49, 26.21, 26.12.
HRMS (ESI) m/z ([M+Na]+) Calcd for C16H22O2Na: 269.1512; Found:269.1512.
dimethyl 2-cyclohexylsuccinate (3s)

According to General Procedure C, 48.2 mg cyclotrimethylgermane and 28.8 mg dimethylfumarate were
20/1) to give 38.7 mg title product as a pale yellow oil, 85% yield.
1
H NMR (400 MHz, CDCl3) δ 3.70 (s, 3H), 3.67 (s, 3H), 2.78 – 2.66 (m, 2H), 2.46 (dt, J = 13.1, 8.9
Hz, 1H), 1.80 – 1.69 (m, 2H), 1.69 – 1.54 (m, 4H), 1.31 – 0.94 (m, 5H).
13
C NMR (101 MHz, CDCl3) δ 175.03, 173.01, 51.77, 51.62, 47.01, 39.94, 33.23, 30.63, 30.13, 26.28,
26.13.
S18
2-cyclohexylsuccinonitrile (3t)
According to General Procedure C, 48.2 mg cyclotrimethylgermane and 15.6 mg fumaronitrile were used.
The crude product was purified by flash column chromatography (petroleum ether/ethyl acetate 8/1) to
give 23.7 mg title product as a colorless crystal, 73% yield.
1
H NMR (400 MHz, CDCl3) δ 2.85 – 2.66 (m, 3H), 1.94 – 1.69 (m, 5H), 1.39 – 1.09 (m, 6H).
13
C NMR (101 MHz, CDCl3) δ 118.12, 115.81, 38.44, 34.72, 30.98, 28.75, 25.65, 25.59, 25.44, 18.71.
HRMS (ESI) m/z ([M+Na]+) Calcd for C10H14N2Na: 185.1049; Found:185.1062.
ethyl 3-cyclohexyl-2-phenylpropanoate (3u)

According to General Procedure C, 48.2 mg cyclotrimethylgermane and 35.2 mg ethyl 2-phenylacrylate
acetate 20/1) to give 40.8 mg title product as a pale yellow thick oil, 78% yield.
1
H NMR (400 MHz, CDCl3) δ 7.36 – 7.15 (m, 5H), 4.21 – 3.98 (m, 2H), 3.67 (t, J = 7.8 Hz, 1H), 1.97
(ddd, J = 13.7, 8.4, 6.9 Hz, 1H), 1.81 – 1.51 (m, 6H), 1.29 – 1.04 (m, 7H), 0.95 – 0.82 (m, 2H).
13
C NMR (101 MHz, CDCl3) δ 174.35, 139.67, 128.53, 127.93, 127.03, 60.61, 48.94, 41.18, 35.35,
33.26, 33.05, 26.51, 26.15, 26.12, 14.15.
2-(cyclohexyl(p-tolyl)methyl)malononitrile (3v)
According to General Procedure C, 48.2 mg cyclotrimethylgermane and 33.6 mg 2-(4-
methylbenzylidene)malononitrile were used. The crude product was purified by flash column
chromatography (petroleum ether/ethyl acetate 8/1) to give 49.3 mg title product as a pale yellow syrup,
98% yield.
1
H NMR (400 MHz, CDCl3) δ 7.20 (s, 4H), 4.17 (d, J = 5.4 Hz, 1H), 2.85 (dd, J = 9.7, 5.5 Hz, 1H),
2.36 (s, 3H), 2.06 – 1.94 (m, 1H), 1.91 (dt, J = 12.3, 3.2 Hz, 1H), 1.84 (ddt, J = 14.5, 5.0, 2.6 Hz, 1H),
1.71 – 1.61 (m, 2H), 1.49 (dd, J = 12.4, 3.8 Hz, 1H), 1.37 (qt, J = 12.8, 3.5 Hz, 1H), 1.22 – 0.97 (m,
3H), 0.86 – 0.75 (m, 1H).
13
C NMR (101 MHz, CDCl3) δ 138.53, 133.60, 129.79, 128.17, 112.33, 112.01, 52.02, 39.20, 31.22,
30.55, 27.22, 25.86, 25.83, 25.74, 21.15.
HRMS (ESI) m/z ([M+Na]+) Calcd for C17H20N2Na: 275.1524; Found:275.1505.
3-cyclohexyl-1-phenylpyrrolidine-2,5-dione (3w)
S19
According to General Procedure C, 48.2 mg cyclotrimethylgermane and 34.6 mg N-phenyl-maleimide
acetate 10/1) to give 25.6 mg title product as a pale yellow syrup, 50% yield.
1
H NMR (400 MHz, CDCl3) δ 7.51 – 7.43 (m, 2H), 7.42 – 7.34 (m, 1H), 7.31 – 7.23 (m, 3H), 2.94 (dt,
J = 9.5, 4.0 Hz, 1H), 2.86 (dd, J = 18.0, 9.4 Hz, 1H), 2.67 (dd, J = 18.0, 4.0 Hz, 1H), 2.06 (dtt, J = 11.5,
7.0, 3.4 Hz, 1H), 1.85 – 1.74 (m, 3H), 1.74 – 1.67 (m, 1H), 1.60 (dd, J = 10.4, 4.9 Hz, 1H), 1.39 – 1.07
(m, 5H).
13
C NMR (101 MHz, CDCl3) δ 178.44, 175.98, 131.96, 129.15, 128.58, 126.50, 45.48, 39.22, 31.35,
30.44, 27.66, 26.20, 25.99, 25.89.
HRMS (ESI) m/z ([M+H]+) Calcd for C16H20NO2: 258.1494; Found:258.1495.
Ethyl 4-cyclohexyl-2-oxochromane-3-carboxylate (3x)

According to General Procedure C, 48.2 mg cyclotrimethylgermane and 43.6 mg ethyl coumarin-3-
carboxylate were used. The crude product was purified by flash column chromatography (petroleum
ether/ethyl acetate 8/1) to give 31.6 mg title product as a yellow syrup, 52% yield; > 20:1 d.r., relative
stereochemistry of 8 was established according to the literature.[9]
1
H NMR (400 MHz, CDCl3) δ 7.29 – 7.24 (m, 1H), 7.15 – 7.05 (m, 3H), 4.11 – 3.94 (m, 2H), 3.93 (d,
J = 1.7 Hz, 1H), 3.11 (dd, J = 8.1, 1.8 Hz, 1H), 1.85 (d, J = 12.4 Hz, 1H), 1.80 – 1.73 (m, 1H), 1.73 –
1.67 (m, 1H), 1.66 – 1.56 (m, 2H), 1.42 (dtd, J = 11.4, 8.1, 3.8 Hz, 1H), 1.22 – 1.08 (m, 3H), 1.07 –
0.93 (m, 5H).
13
C NMR (101 MHz, CDCl3) δ 167.67, 165.15, 151.06, 129.86, 128.70, 124.28, 123.18, 116.92,
62.09, 49.82, 46.09, 41.19, 30.55, 29.98, 26.07, 25.97, 25.96, 13.73.
5-(methoxycarbonyl)-3,3-dimethylhex-5-enoic acid diosgenin ester (3y)

According to General procedure C, 60.2 mg (0.1 mmol) 1n, 48.1 mg (0.2 mmol) methyl 2-
((phenylsulfonyl)methyl)acrylate and 1.5 mg (3 %mol) 3,6-di-tert-butyl-9-mesityl-10-methylacridin-10-
ium tetrafluoroborate were added to a 10 mL screw-cap tube equipped with a stir bar. After vacuumed
and backfilled with argon for 3 times, 0.4 mL DCE, 40μL MeOH and 40μL MeCN were added. The
tube was sealed with a Teflon stopper and irradiated with a 8 W 460 nm LED lamp (1 cm) for 24 hours.
The reaction mixture was then extracted with ethyl acetate and water. Organic layer was separated, dried
over Na2SO4, and concentrated under reduced pressure. The product was purified by flash column
chromatography (petroleum ether/ethyl acetate 20/1) to give 17.7 mg title product as a white solid, 30%
yield.
S20
1
H NMR (400 MHz, CDCl3) δ 6.26 (d, J = 1.8 Hz, 1H), 5.60 (d, J = 1.7 Hz, 1H), 5.38 (d, J = 5.0 Hz,
1H), 4.62 (dtd, J = 11.0, 7.5, 6.9, 4.0 Hz, 1H), 4.41 (td, J = 7.9, 6.5 Hz, 1H), 3.74 (s, 3H), 3.47 (ddd, J
= 10.8, 4.4, 2.0 Hz, 1H), 3.38 (t, J = 10.7 Hz, 1H), 2.44 (s, 2H), 2.35 – 2.29 (m, 2H), 2.18 (s, 2H), 2.03
– 1.95 (m, 2H), 1.90 – 1.82 (m, 3H), 1.80 – 1.75 (m, 1H), 1.75 – 1.70 (m, 1H), 1.67 (t, J = 5.1 Hz, 1H),
1.65 – 1.60 (m, 5H), 1.57 – 1.42 (m, 4H), 1.33 – 1.27 (m, 1H), 1.23 – 1.05 (m, 5H), 1.04 (s, 3H), 0.99 –
0.95 (m, 9H), 0.81 – 0.77 (m, 6H).
13
C NMR (101 MHz, CDCl3) δ 171.54, 168.51, 139.70, 137.77, 128.48, 122.37, 109.30, 80.82, 73.63,
66.85, 62.05, 56.42, 51.94, 49.93, 45.88, 42.38, 41.61, 40.25, 39.72, 38.21, 36.97, 36.75, 34.20, 32.03,
31.84, 31.38, 30.30, 28.80, 27.89, 26.82, 20.81, 19.36, 17.15, 16.30, 14.54.
HRMS (ESI) m/z ([M+H]+) Calcd for C27H57O6: 597.4155; Found: 597.4158.
Methyl 2-methylene-4-phenylbutanoate (3z)

Methyl 2-((phenylsulfonyl)methyl)acrylate was prepared as reported[10]. According to General Procedure
C, 41.8 mg (0.2 mmol) benzyltrimethylgermane and 57.7 mg (0.24 mmol) methyl 2-
((phenylsulfonyl)methyl)acrylate were used. The crude product was purified by flash column
chromatography (petroleum ether/ethyl acetate 20/1) to give 21.6 mg title product as a pale yellow oil,
57% yield.
1
(t, J = 1.4 Hz, 1H), 3.76 (s, 3H), 2.79 (dd, J = 9.5, 6.2 Hz, 2H), 2.62 (dd, J = 9.4, 6.4 Hz, 2H).
13
C NMR (101 MHz, CDCl3) δ 167.60, 141.37, 139.81, 128.48, 128.41, 128.38, 128.33, 125.96,
125.44, 51.85, 34.84, 33.87.
HRMS (ESI) m/z ([M+H]+) Calcd for C12H15O2: 191.1072; Found:191.1064.
Methyl 2-(cyclohexylmethyl)acrylate (3aa)

According to General Procedure C, 40.2 mg (0.2 mmol) cyclotrimethylgermane and 57.7 mg (0.24 mmol)
methyl 2-((phenylsulfonyl)methyl)acrylate were used. The crude product was purified by flash column
chromatography (petroleum ether/ethyl acetate 20/1) to give 24.4 mg title product as a pale yellow oil,
67% yield.
1
H NMR (400 MHz, CDCl3) δ 6.15 (d, J = 1.7 Hz, 1H), 5.48 (q, J = 1.3 Hz, 1H), 3.75 (s, 3H), 2.19
(dd, J = 7.1, 1.1 Hz, 2H), 1.75 – 1.60 (m, 5H), 1.30 – 1.10 (m, 4H), 0.93 – (m, 2H).
13
C NMR (101 MHz, CDCl3) δ 168.01, 139.15, 125.78, 51.77, 39.97, 36.55, 33.06, 26.51, 26.22.
HRMS (EI) m/z (M+•) Calcd for C11H18O2: 182.13068; Found:182.13002.
Methyl 2-((1-butylcyclohexyl)methyl)acrylate (3ab)

According to General Procedure C, 51.4 mg (0.2 mmol) (1-butylcyclohexyl)trimethylgermane and 57.7
mg (0.24 mmol) methyl 2-((phenylsulfonyl)methyl)acrylate were used. The crude product was purified
by flash column chromatography (petroleum ether/ethyl acetate 20/1) to give 34.6 mg title product as a
S21
pale yellow oil, 73% yield.
1
H NMR (400 MHz, CDCl3) δ 6.15 (d, J = 1.8 Hz, 1H), 5.42 (d, J = 1.7 Hz, 1H), 3.73 (s, 3H), 2.32 (s,
2H), 1.49 – 1.33 (m, 5H), 1.30 – 1.11 (m, 11H), 0.90 (t, J = 6.8 Hz, 3H).
13
C NMR (101 MHz, CDCl3) δ 169.03, 138.53, 127.02, 51.84, 36.23, 34.92, 26.21, 25.13, 23.60,
21.68, 14.25.
HRMS (ESI) m/z ([M+H]+) Calcd for C15H27O2: 239.2011; Found:239.2009.
3.3 General procedure of Ni catalyzed photoredox cross-coupling reaction and characterization of

the products
Aryl bromide were purchased from commercial source unless otherwise noted.
General Procedure D:
To an oven-dried 10 mL screw-capped tube equipped with stir bar was charge with 2.0 mg (3% mmol)
Ni(phen)Cl2 and 3.1 mg (3% mmol) 3,6-di-tert-butyl-9-mesityl-10-methylacridin-10-ium
tetrafluoroborate. The tube was vacuumed and backfilled with argon for three cycles. 2.0 mL anhydrous
MeCN was added followed by addition of 0.24 mmol alkyltrimethylgermane and 0.2 mmol arylbromide.
The tube was sealed with a Teflon stopper and irradiated with an 8 W 460 nm LED lamp (1 cm) for 24
hours. The reaction mixture was then extracted with ethyl acetate and water. Organic layer was separated,
dried over Na2SO4, and concentrated under reduced pressure. The product was purified by flash column
chromatography.
4-Cyclohexylbenzonitrile (4a)
According to General Procedure D, 48.2 mg cyclohexyltrimethylgermane and 36.4 mg 4-
bromobenzonitrile were used. The crude product was purified by flash column chromatography
(petroleum ether/ethyl acetate 20/1) to give 19.7 mg title product as a colorless thick oil, 53% yield.
1
1.79 (m, 4H), 1.82 – 1.71 (m, 1H), 1.45 – 1.32 (m, 4H), 1.29 – 1.16 (m, 2H).
13
C NMR (101 MHz, CDCl3) δ 153.51, 132.21, 127.68, 119.25, 109.55, 44.77, 34.00, 26.62, 25.93.
HRMS (EI) m/z (M+•) Calcd for C13 H15N: 185.12045; Found:185.11967.
1-(4-cyclohexylphenyl)ethan-1-one (4b)
According to General Procedure D, 48.2 mg cyclohexyltrimethylgermane and 39.8 mg 4'-
bromoacetophenone were used. The crude product was purified by flash column chromatography
1
H NMR (400 MHz, CDCl3) δ 7.92 – 7.86 (m, 2H), 7.31 – 7.27 (m, 2H), 2.58 (s, 4H), 1.91 – 1.81 (m,
S22
4H), 1.76 (dtt, J = 12.5, 3.2, 1.5 Hz, 1H), 1.49 – 1.34 (m, 4H), 1.31 – 1.20 (m, 1H).
13
C NMR (101 MHz, CDCl3) δ 197.90, 153.78, 135.05, 128.56, 127.06, 44.70, 34.12, 26.73, 26.57,
26.04.
HRMS (ESI) m/z ([M+H]+) Calcd for C14H19O: 203.1436; Found: 203.1440.
Methyl 4-cyclohexylbenzoate (4c)

According to General Procedure D, 48.2 mg cyclohexyltrimethylgermane and 43.0 mg methyl 4-
bromobenzoate were used. The crude product was purified by flash column chromatography (petroleum
ether/ethyl acetate 30/1) to give 25.9 mg title product as a colorless thick oil, 60% yield.
1
H NMR (400 MHz, CDCl3) δ 7.98 – 7.91 (m, 2H), 7.29 – 7.25 (m, 2H), 3.90 (s, 3H), 2.56 (tt, J =
11.4, 3.6 Hz, 1H), 1.92 – 1.81 (m, 4H), 1.79 – 1.72 (m, 1H), 1.49 – 1.32 (m, 4H), 1.26 (tdd, J = 14.7,
7.6, 4.2 Hz, 1H).
13
C NMR (101 MHz, CDCl3) δ 167.22, 153.49, 129.70, 127.73, 126.88, 51.96, 44.70, 34.15, 26.75,
26.06.
4-cyclohexylbenzaldehyde (4d)
bromobenzaldehyde were used. The crude product was purified by flash column chromatography
(petroleum ether/ethyl acetate 30/1) to give 25.2mg title product as a colorless oil, 67% yield.
1
H NMR (400 MHz, Chloroform-d) δ 9.96 (m, 1H), 7.86 – 7.74 (m, 2H), 7.36 (d, J = 7.9 Hz, 2H),
2.59 (tt, J = 8.4, 3.4 Hz, 1H), 1.92 – 1.83 (m, 4H), 1.77 (dtt, J = 12.8, 2.9, 1.4 Hz, 1H), 1.50 – 1.35 (m,
4H), 1.31 – 1.24 (m, 1H).
13
C NMR (101 MHz, CDCl3) δ 192.07, 155.39, 134.54, 129.98, 127.54, 44.92, 34.07, 26.69, 26.01.
1-cyclohexyl-4-(methylsulfonyl)benzene (4e)
According to General Procedure D, 48.2 mg cyclohexyltrimethylgermane and 47.0 mg 4-bromophenyl
methyl sulfone were used. The crude product was purified by flash column chromatography (petroleum
ether/ethyl acetate 5/1) to give 28.0 mg title product as a white solid, 59% yield.
1
H NMR (400 MHz, CDCl3) δ 7.91 – 7.76 (m, 2H), 7.49 – 7.32 (m, 2H), 3.04 (s, 3H), 2.61 (td, J =
9.9, 8.9, 5.0 Hz, 1H), 1.94 – 1.81 (m, 2H), 1.81 – 1.71 (m, 1H), 1.49 – 1.33 (m, 4H), 1.33 – 1.20 (m,
1H).
13
C NMR (101 MHz, CDCl3) δ 154.47, 137.95, 127.83, 127.46, 44.65, 44.59, 34.10, 26.64, 25.93.
HRMS (ESI) m/z ([M+H]+) Calcd for C13H19O2S: 239.1106; Found: 239.1111.
S23
4-cyclohexylbenzenesulfonamide (4f)
Bromobenzenesulfonamide were used. The crude product was purified by flash column chromatography
(dichloromethane/tetrahydrofuran 10/1) to give 24.3 mg title product as a white solid, 51% yield.
1
H NMR (400 MHz, Chloroform-d) δ 7.87 – 7.81 (m, 2H), 7.38 – 7.32 (m, 2H), 4.87 (s, 2H), 2.64 –
2.53 (m, 1H), 1.94 – 1.80 (m, 4H), 1.82 – 1.72 (m, 1H), 1.48 – 1.33 (m, 4H), 1.32 – 1.23 (m, 1H).
13
C NMR (101 MHz, CDCl3) δ 153.56, 139.19, 127.64, 126.56, 44.58, 34.14, 26.66, 25.96.
HRMS (ESI) m/z ([M+H]+) Calcd for C12H18NO2S: 240.1058; Found: 240.1059.
3-cyclohexylbenzonitrile (4g)
(petroleum ether/ethyl acetate 30/1) to give 17.4 mg title product as a colorless thick oil, 47% yield. The
spectroscopic data are in agreement with those reported in the literature.
1
2.47 (m, 1H), 1.91 – 1.80 (m, 4H), 1.80 – 1.72 (m, 1H), 1.46 – 1.32 (m, 4H), 1.29 – 1.20 (m, 1H).
13
C NMR (101 MHz, CDCl3) δ 149.28, 131.61, 130.55, 129.60, 129.07, 119.29, 112.22, 44.18, 34.15,
26.65, 25.92.
HRMS (ESI) m/z ([M+H]+) Calcd for C13H16N: 186.1283; Found: 186.1282.
1-cyclohexyl-3,5-bis(trifluoromethyl)benzene (4h)
According to General Procedure D, 48.2 mg cyclohexyltrimethylgermane and 58.6 mg 3,5-
bis(trifluoromethyl)bromobenzene were used. The crude product was purified by flash column
chromatography (petroleum ether) to give 32.4 mg title product as a colorless oil, 55% yield. The
spectroscopic data are in agreement with those reported in the literature.[11]
1
H NMR (400 MHz, CDCl3) δ 7.70 (s, 1H), 7.65 (d, J = 1.7 Hz, 2H), 2.65 (tt, J = 11.4, 3.0 Hz, 1H),
1.95 – 1.84 (m, 4H), 1.82 – 1.74 (m, 1H), 1.51 – 1.36 (m, 4H), 1.33 – 1.23 (m, 1H).
19
F NMR (376 MHz, CDCl3) δ -62.77.
13
C NMR (101 MHz, CDCl3) δ 150.26, 131.41 (q, J = 32.3 Hz), 127.09 (d, J = 2.0 Hz), 123.54 (q, J =
273.7 Hz), 119.85 (q, J = 4.1 Hz), 44.34, 34.11, 26.55, 25.80.
S24
2-cyclohexylbenzonitrile (4i)
1
H NMR (400 MHz, CDCl3) δ 7.60 (dd, J = 7.7, 1.4 Hz, 1H), 7.53 (td, J = 7.7, 1.4 Hz, 1H), 7.37 (dd, J
= 8.1, 1.1 Hz, 1H), 7.26 (dd, J = 15.2, 1.2 Hz, 2H), 2.98 (ddt, J = 11.6, 8.2, 3.4 Hz, 1H), 1.93 – 1.83
(m, 4H), 1.83 – 1.74 (m, 1H), 1.55 – 1.38 (m, 4H), 1.31 – 1.23 (m, 1H).
13
C NMR (101 MHz, CDCl3) δ 151.50, 132.92, 132.89, 126.52, 126.26, 118.28, 111.79, 42.73, 33.67,
26.58, 25.91.
1-(2-cyclohexylphenyl)ethan-1-one (4j)
According to General Procedure D, 48.2 mg cyclohexyltrimethylgermane and 39.8 mg 2'-
bromoacetophenone were used. The crude product was purified by flash column chromatography
(petroleum ether/ethyl acetate 30/1) to give 15.6 mg title product as a pale yellow oil, 39% yield.
1
H NMR (400 MHz, CDCl3) δ 7.49 – 7.44 (m, 1H), 7.41 – 7.36 (m, 2H), 7.22 (ddd, J = 7.7, 6.0, 2.5
Hz, 1H), 3.10 – 2.96 (m, 1H), 2.57 (s, 3H), 1.90 – 1.78 (m, 4H), 1.78 – 1.71 (m, 1H), 1.47 – 1.34 (m,
4H), 1.31 – 1.19 (m, 1H).
13
C NMR (101 MHz, CDCl3) δ 203.84, 146.61, 139.13, 130.93, 127.66, 127.14, 125.37, 39.97, 34.56,
30.81, 26.90, 26.24.
HRMS (ESI) m/z ([M+Na]+) Calcd for C14H18ONa: 225.1255; Found: 225.1260.
Methyl 2-cyclohexylbenzoate (4k)

According to General Procedure D, 48.2 mg cyclohexyltrimethylgermane and 43.0 mg methyl 2-
ether/ethyl acetate 30/1) to give 7.5 mg title product as a pale yellow oil, 26% yield.
1
H NMR (400 MHz, CDCl3) δ 7.73 (dd, J = 7.8, 1.5 Hz, 1H), 7.44 (ddd, J = 8.3, 7.2, 1.5 Hz, 1H), 7.39
(dd, J = 7.9, 1.5 Hz, 1H), 7.21 (ddd, J = 7.7, 7.1, 1.5 Hz, 1H), 3.90 (s, 3H), 3.30 (tt, J = 8.2, 3.5 Hz,
1H), 1.91 – 1.80 (m, 4H), 1.79 – 1.72 (m, 1H), 1.47 – 1.36 (m, 4H), 1.30 – 1.23 (m, 1H).
13
C NMR (101 MHz, CDCl3) δ 168.88, 148.70, 131.66, 129.95, 129.87, 126.86, 125.40, 52.01, 40.25,
34.41, 27.01, 26.29.
S25
5-cyclohexylpyrimidine (4l)
bromopyrimidine were used. The crude product was purified by flash column chromatography
(petroleum ether/ethyl acetate 10/1) to give 9.3 mg title product as a colorless oil, 29% yield.
1
H NMR (400 MHz, CDCl3) δ 9.07 (s, 1H), 8.60 (s, 2H), 2.55 (ddq, J = 15.0, 7.6, 3.3 Hz, 1H), 1.97 –
1.82 (m, 4H), 1.79 (dddt, J = 12.4, 4.6, 3.1, 1.6 Hz, 1H), 1.51 – 1.34 (m, 4H), 1.27 (ddt, J = 15.9, 9.6,
4.2 Hz, 1H).
13
C NMR (101 MHz, CDCl3) δ 156.66, 155.59, 140.18, 39.88, 33.68, 26.46, 25.70.
4-cyclohexyl-2,8-bis(trifluoromethyl)quinolone (4m)
According to General Procedure D, 48.2 mg cyclohexyltrimethylgermane and 68.8 mg 4-bromo-2,8-
bis(trifluoromethyl)quinoline were used. The crude product was purified by flash column
chromatography (petroleum ether/ethyl acetate 10/1) to give 50.8 mg title product as a pale yellow solid,
84% yield.
1
H NMR (400 MHz, CDCl3) δ 8.35 (dd, J = 8.8, 1.3 Hz, 1H), 8.14 (d, J = 7.2 Hz, 1H), 7.75 – 7.66 (m,
2H), 3.39 (tt, J = 8.3, 3.4 Hz, 1H), 2.06 – 1.93 (m, 4H), 1.92 – 1.83 (m, 1H), 1.66 – 1.49 (m, 4H), 1.45
– 1.32 (m, 1H).
13
C NMR (101 MHz, CDCl3) δ 156.53, 148.34 (q, J = 34.3 Hz), 143.92, 129.48 (q, J = 30.3 Hz),
128.57 (q, J = 6.1 Hz), 127.89, 127.42, 126.69, 123.70 (q, J = 274.7 Hz), 121.41 (q, J = 276.7 Hz),
114.06 (q, J = 2.0 Hz), 39.48, 33.57, 26.72, 26.01.
19
F NMR (376 MHz, CDCl3) δ -60.23, -67.92.
HRMS (ESI) m/z ([M+H]+) Calcd for C17H16F6N: 348.1187; Found: 348.1189.
4-cyclohexyl-2-(trifluoromethyl)pyridine (4n)
According to General Procedure D, 48.2 mg cyclohexyltrimethylgermane and 45.2 mg 4-bromo-2-
trifluoromethylpyridine were used. The crude product was purified by flash column chromatography
1
H NMR (500 MHz, Chloroform-d) δ 8.61 (d, J = 5.1 Hz, 1H), 7.52 (d, J = 1.7 Hz, 1H), 7.32 (dd, J =
5.2, 1.6 Hz, 1H), 2.60 (tt, J = 11.4, 3.2 Hz, 1H), 1.95 – 1.84 (m, 4H), 1.79 (dtt, J = 12.3, 4.2, 2.0 Hz,
1H), 1.48 – 1.35 (m, 4H), 1.32 – 1.22 (m, 1H).
13
C NMR (126 MHz, CDCl3) δ 158.71, 149.89, 148.20 (q, J = 34.0 Hz), 124.98, 121.74 (q, J = 274.7
Hz), 119.16 (q, J = 2.9 Hz), 43.96, 33.43, 26.39, 25.77.
S26
19
F NMR (376 MHz, CDCl3) δ -67.88.
HRMS (ESI) m/z ([M+H]+) Calcd for C12H15F3N: 230.1157; Found: 230.1163.
4-benzylbenzonitrile (4o)
According to General Procedure D, 50.1 mg benzyltrimethylgermane and 36.4 mg 4-bromobenzonitrile
acetate 30/1) to give 35.1 mg title product as a colorless thick oil, 93% yield.
1
H NMR (400 MHz, CDCl3) δ 7.59 – 7.53 (m, 2H), 7.34 – 7.21 (m, 5H), 7.16 (dd, J = 6.8, 1.8 Hz,
2H), 4.03 (s, 2H).
13
C NMR (101 MHz, CDCl3) δ 146.76, 139.35, 132.32, 129.66, 128.98, 128.79, 126.69, 119.02,
110.06, 41.99.
HRMS (EI) m/z (M+•) Calcd for C14H11N: 193.08915; Found:193.08845
Methyl 4-benzylbenzoate (4p)

According to General Procedure D, 50.1 mg benzyltrimethylgermane and 43.0 mg methyl 4-
ether/ethyl acetate 30/1) to give 58.4 mg title product as a yellow syrup, 92% yield.
1
H NMR (400 MHz, CDCl3) δ 7.89 (dd, J = 7.8, 1.5 Hz, 1H), 7.42 (td, J = 7.6, 1.5 Hz, 1H), 7.30 –
7.23 (m, 3H), 7.22 – 7.16 (m, 2H), 7.16 – 7.12 (m, 2H), 4.38 (s, 2H), 3.81 (s, 3H).
13
C NMR (101 MHz, CDCl3) δ 168.07, 142.15, 140.89, 131.97, 131.56, 130.67, 129.93, 128.88,
128.32, 126.24, 125.92, 51.92, 39.60.
2-benzylnaphthalene (4q)
According to General Procedure D, 50.1 mg benzyltrimethylgermane and 41.4 mg 1-bromonaphthalene
were used. The crude product was purified by flash column chromatography (petroleum ether) to give
31.2 mg title product as a colorless syrup, 71% yield. The spectroscopic data are in agreement with those
reported in the literature.[12]
1
– 7.36 (m, 3H), 7.30 – 7.22 (m, 3H), 7.20 – 7.15 (m, 3H), 4.44 (s, 2H).
13
C NMR (101 MHz, CDCl3) δ 140.69, 136.68, 134.00, 132.20, 128.80, 128.73, 128.51, 127.40,
127.21, 126.11, 126.03, 125.61, 124.34, 39.10.
1-benzyl-3,5-dimethoxybenzenee (4r)
S27
According to General Procedure D, 50.1 mg benzyltrimethylgermane and 43.4 mg 3,5-
Bis(trifluoromethyl)bromobenzene were used. The crude product was purified by flash column
chromatography (petroleum ether/ethyl acetate 30/1) to give 24.3 mg title product as a colorless syrup,
53% yield.
1
H NMR (400 MHz, Chloroform-d) δ 7.31 – 7.24 (m, 2H), 7.22 – 7.15 (m, 3H), 6.37 – 6.33 (m, 2H),
6.33 – 6.29 (m, 1H), 3.91 (s, 2H), 3.74 (s, 6H).
13
C NMR (101 MHz, CDCl3) δ 160.86, 143.46, 140.76, 128.92, 128.49, 126.17, 107.14, 97.99, 55.27,
42.21.
Methyl 2-benzylbenzoate (4s)

According to General Procedure D, 50.1 mg benzyltrimethylgermane and 43.0 mg methyl 2-
ether/ethyl acetate 30/1) to give 34.5 mg title product as a pale yellow syrup, 76% yield.
1
7.19 (m, 1H), 7.19 – 7.14 (m, 2H), 4.02 (s, 2H), 3.89 (s, 3H).
13
C NMR (101 MHz, CDCl3) δ 167.05, 146.51, 140.11, 129.82, 128.94, 128.60, 128.08, 126.37,
52.01, 41.91.
(2-benzylphenyl)(phenyl)methanone (4t)
According to General Procedure D, 50.1 mg benzyltrimethylgermane and 52.2 mg 2-
bromobenzophenone were used. The crude product was purified by flash column chromatography
(petroleum ether/ethyl acetate 30/1) to give 44.4 mg title product as a yellow syrup, 82% yield.
1
H NMR (400 MHz, CDCl3) δ 7.74 – 7.69 (m, 2H), 7.54 (ddt, J = 8.7, 7.0, 1.3 Hz, 1H), 7.43 – 7.37
(m, 3H), 7.31 – 7.25 (m, 3H), 7.19 – 7.13 (m, 2H), 7.11 – 7.05 (m, 3H), 4.06 (s, 2H).
13
C NMR (101 MHz, CDCl3) δ 198.60, 140.47, 140.13, 138.83, 137.70, 133.15, 130.84, 130.34,
130.18, 130.10, 129.21, 128.65, 128.33, 128.31, 126.04, 125.62, 38.86.
4-benzyl-2-methyl-2H-indazole (4u)
According to General Procedure D, 50.1 mg benzyltrimethylgermane and 42.2 mg 4-bromo-2-methyl-
2h-indazole were used. The crude product was purified by flash column chromatography (petroleum
ether/ethyl acetate 5/1) to give 29.3 mg title product as a colorless syrup, 66% yield.
1
H NMR (400 MHz, Chloroform-d) δ 7.65 (s, 1H), 7.57 (d, J = 8.7 Hz, 1H), 7.30 – 7.16 (m, 6H), 6.87
(dd, J = 6.7, 1.0 Hz, 1H), 4.18 (s, 2H), 4.11 (s, 3H).
S28
13
C NMR (101 MHz, CDCl3) δ 149.32, 140.11, 132.97, 128.81, 128.45, 126.24, 126.10, 122.86,
122.50, 121.34, 115.40, 40.25, 40.22.
7-phenylbicyclo[4.2.0]octa-1(6),2,4-triene (4v)
According to General Procedure D, 53.0 mg bicyclo[4.2.0]octa-1,3,5-trien-7-yltrimethylgermane and
36.4 mg 4-bromobenzonitrile were used. The crude product was purified by flash column
chromatography (petroleum ether) to give 20.4 mg title product as a colorless thick oil, 57% yield.
1
H NMR (400 MHz, CDCl3) δ 7.34 – 7.26 (m, 6H), 7.22 – 7.12 (m, 4H), 4.70 (dd, J = 5.7, 2.8 Hz,
1H), 3.78 – 3.65 (m, 1H), 3.09 (dd, J = 13.9, 2.7 Hz, 1H).
13
C NMR (101 MHz, CDCl3) δ 147.68, 144.15, 142.84, 128.43, 127.64, 127.13, 126.93, 126.41,
123.25, 122.75, 47.48, 39.96.
HRMS (EI) m/z (M+•) Calcd for C14H12: 180.09390; Found: 180.09310.
4-(bicyclo[4.2.0]octa-1(6),2,4-trien-7-yl)benzonitrile (4w)
31.4 mg bromobenzene were used. The crude product was purified by flash column chromatography
1
H NMR (400 MHz, CDCl3) δ 7.59 (d, J = 8.0 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.34 – 7.26 (m, 2H),
7.20 – 7.11 (m, 2H), 4.73 (dd, J = 5.8, 2.6 Hz, 1H), 3.77 (dd, J = 14.0, 5.7 Hz, 1H), 3.07 (dd, J = 14.0,
2.7 Hz, 1H).
13
C NMR (101 MHz, CDCl3) δ 148.40, 146.14, 143.72, 132.34, 128.21, 127.75, 127.52, 123.48,
122.71, 119.07, 110.23, 47.29, 39.89.
HRMS (EI) m/z (M+•) Calcd for C15H11N: 205.08915; Found:205.08839
7-(4-(trifluoromethyl)phenyl)bicyclo[4.2.0]octa-1(6),2,4-triene (4x)
45.0 mg 4-bromobenzotrifluoride were used. The crude product was purified by flash column
chromatography (petroleum ether) to give 40.3 mg title product as a colorless thick oil, 81% yield.
1
7.11 (m, 2H), 4.73 (dd, J = 5.8, 2.6 Hz, 1H), 3.79 – 3.69 (m, 1H), 3.12 – 3.01 (m, 1H).
19
F NMR (376 MHz, CDCl3) δ -62.31.
S29
13
C NMR (101 MHz, CDCl3) δ 146.90, 146.72, 143.88, 128.88 (q, J =32.3), 128.02, 127.40, 127.27,
125.39 (q, J =4.0 Hz), 123.41, 122.71, 47.14, 39.91, 29.74.
HRMS (EI) m/z (M+•) Calcd for C15H11F3: 248.08128; Found: 248.08120.
2-(4-(bicyclo[4.2.0]octa-1(6),2,4-trien-7-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4y)
56.6 mg 4-bromophenylboronic acid pinacol ester were used. The crude product was purified by flash
column chromatography (petroleum ether/ethyl acetate 20/1) to give 39.2 mg title product as a colorless
thick oil, 64% yield.
1
H NMR (400 MHz, CDCl3) δ 7.75 (d, J = 7.9 Hz, 2H), 7.32 – 7.25 (m, 5H), 7.15 (dq, J = 7.3, 4.4, 2.7
Hz, 2H), 4.70 (dd, J = 5.9, 2.7 Hz, 1H), 3.72 (dd, J = 14.0, 5.7 Hz, 1H), 3.08 (dd, J = 14.0, 2.7 Hz, 1H),
1.33 (s, 13H).
13
C NMR (101 MHz, CDCl3) δ 147.47, 146.13, 144.12, 135.01, 127.66, 127.17, 126.37, 123.24,
122.76, 83.71, 47.65, 39.92, 24.87, 24.84.
HRMS (EI) m/z (M+•) Calcd for C20H23BO2: 306.17911; Found:306.17839
1-(4-(bicyclo[4.2.0]octa-1(6),2,4-trien-7-yl)phenyl)ethan-1-one (4z)
39.8 mg 4-bromoacetophenone ester were used. The crude product was purified by flash column
chromatography (petroleum ether/ethyl acetate 20/1) to give 43.6 mg title product as a colorless thick oil,
98% yield.
1
H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 8.2 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.31 – 7.27 (m, 2H),
7.20 – 7.13 (m, 2H), 4.74 (dd, J = 5.9, 2.6 Hz, 1H), 3.77 (dd, J = 14.0, 5.7 Hz, 1H), 3.10 (dd, J = 13.9,
2.7 Hz, 1H), 2.59 (s, 3H).
13
C NMR (101 MHz, CDCl3) δ 197.83, 148.49, 146.78, 143.89, 135.52, 128.65, 127.96, 127.37,
127.14, 123.38, 122.72, 47.33, 39.86, 26.63.
HRMS (EI) m/z (M+•) Calcd for C16H14O: 222.10447; Found:222.10382
4-phenethylbenzaldehyde (4aa)
According to General Procedure D, 53.5 mg trimethyl(phenethyl)germane and 37.0 mg 4-
bromobenzaldehyde were used. The crude product was purified by flash column chromatography
(petroleum ether/ethyl acetate 25/1) to give 19.6 mg title product as a pale yellow oil, 47% yield.
1
H NMR (400 MHz, CDCl3) δ 9.97 (s, 1H), 7.81 – 7.76 (m, 2H), 7.33 – 7.25 (m, 4H), 7.23 – 7.17 (m,
S30
1H), 7.17 – 7.12 (m, 2H), 3.03 – 2.91 (m, 4H).
13
C NMR (101 MHz, CDCl3) δ 192.04, 149.07, 140.89, 134.55, 129.91, 129.19, 128.42, 126.16,
38.05, 37.35.
2-phenethylbenzonitrile (4ab)
According to General Procedure D, 53.5 mg trimethyl(phenethyl)germane and 36.4 mg 2-
1
H NMR (400 MHz, CDCl3) δ 7.62 (dd, J = 7.7, 1.4 Hz, 1H), 7.48 (td, J = 7.7, 1.4 Hz, 1H), 7.32 –
7.26 (m, 3H), 7.25 – 7.17 (m, 4H), 3.17 – 3.10 (m, 2H), 2.97 (dd, J = 9.6, 6.4 Hz, 2H).
13
C NMR (101 MHz, CDCl3) δ 145.47, 140.47, 132.83, 132.70, 129.70, 128.53, 128.46, 126.64,
126.26, 118.03, 112.34, 37.15, 36.76.
4. Mechanism studies
4.1 Preparation of 5.
To a 25 mL Schlenk tube was charged with 418.7 mg (4 mmol) GeO2. The flask was then vacuumed
and backfilled with argon for three times. 1.6 mL (30%) concentrated hydrochloric acid and 0.88 mL
(35%) hypophosphorous acid was added. The mixture was stirred at 80 oC for 4 hours before cooled to
room temperature. Another 1.6 mL (35%) concentrated hydrochloric acid was added, followed by 330.0
mg (3.83 mmol) crotonic acid. The mixture was stirred at room temperature for 12 hours. Resulting white
precipitate was filtered and washed with concentrated hydrochloric acid, dried under vacuum and then
transferred to an oven dried Schlenk flask. After vacuumed and backfilled with argon for three times, the
flask was cooled to 0 oC. 4.3 mL anhydrous diethyl ether was added. 15.5 mmol BuMgBr (2 M in Et2O)
was added in a 5-minutes period. The mixture was warmed to reflux for an hour, and then poured into
excess diluted hydrochloric acid (2 M). The mixture was extracted with diethyl ether (10 mL x 3),
combined organic layers was dried over Na2SO4, concentrated under reduced pressure to give crude 3-
(tributylgermyl)butanoic acid as a pale yellow thick oil which was directed used in the next step.
To a screw-capped tube vacuumed and backfilled with argon was charged with 197.2 mg (5.2 mmol)
LiAlH4 and 2.4 mL anhydrous diethyl ether. The mixture was cooled to 0 oC and the crude 3-
(tributylgermyl)butanoic acid obtained above in 6.4 mL diethyl ether was added carefully. The mixture
S31
was warmed to 35 oC and stirred for 5 hours, the reaction was quenched by adding excess NaOH solution ,
extracted with diethyl ether (40 mL x 3) and concentrated under reduced pressure to give the crude
product as a yellow thick oil, which was purified by flash column chromatography (petroleum ether/ethyl
acetate 20/1) to give 792.5 mg colorless thick oil, 62% yield.
1
H NMR (400 MHz, CDCl3) δ 3.73 (ddd, J = 10.4, 8.1, 4.8 Hz, 1H), 3.64 (dt, J = 10.4, 7.4 Hz, 1H),
1.79 (dtd, J = 13.5, 7.8, 3.9 Hz, 1H), 1.55 – 1.43 (m, 3H), 1.37 – 1.27 (m, 12H), 1.15 (dtt, J = 10.3, 6.4,
3.1 Hz, 1H), 1.04 (d, J = 7.2 Hz, 3H), 0.94 – 0.84 (m, 9H), 0.77 – 0.66 (m, 6H).
13
C NMR (101 MHz, CDCl3) δ 61.96, 36.27, 27.59, 26.81, 15.57, 15.52, 13.77, 11.14.
IR v = 3356, 2954, 2920, 2856, 1462, 1421, 1377, 1340, 1294, 1083, 1051, 1002, 990, 964, 884, 691,
650 cm-1.
HRMS (ESI) m/z ([M+Na]+) Calcd for C16H36 GeNaO: 341.1876; Found: 341.1868.
4.2 Competitive radical addition using 5
To an oven-dried 10 mL screw-capped tube equipped with stir bar was charge with 7.7 mg (0.05 mmol)
benzalmalononitrile and 0.8 mg (3% mmol) 3,6-di-tert-butyl-9-mesityl-10-methylacridin-10-ium
tetrafluoroborate. The tube was vacuumed and backfilled with argon for three cycles. 0.2 mL solvent
was added followed by addition of 12.0 mg (0.06 mmol) cyclohexyltrimethylgermane. The tube was
sealed with a Teflon stopper and irradiated using an 8 W 460 nm LED lamp for 24 hours. 12.2 mg
(0.05 mmol) triphenylmethane was added as standard. The mixture was dried under vacuum. The ratio
of the two products was then determined by 1 H NMR. Byproduct was determined by GC-MS.
S32
S33
Figure S2. GC-MS analyze of mechanism experiment byproducts using MeCN/MeOH as the solvent.
S34
Figure S3. GC-MS analyze of mechanism reaction byproducts using DCE as the solvent.
S35
4.3 Cyclic voltammogram
Figure S4. Cyclic voltammogram of cyclohexyltrimethylgermane 1a, [0.01 M] in [0.1 M] TBAPF 6 in

CH3CN. Sweep rate: 20 mV/s. Glassy carbon working electrodes, Ag/AgCl (NaCl saturated) reference
electrodes, Pt auxiliary electrode. Irreversible oxidation. EpA = Eox(1a•+/1a) = +2.05 V; EpA is anodic peak
potential, while Eox value describes the electrochemical properties of 1a.
4.4 Stern-Volmer Fluorescence Quenching Studies
Solutions with [tBu-Acr-Mes]+BF4- concentration at 0.01 mM and different concentrations of 1g in

MeCN were prepared and analyzed in a 10 × 10 mm quartz cuvette. The emission spectra was recorded
using a Hitachi F-4600 fluorescence spectrophotometer equipped with a Xenon pulse lamp. The
excitation wavelength was fixed at 440 nm and the emission light was acquired from 450 nm to 700 nm
(emission light slit regulated to 2.5 nm). For quenching data, the emission wavelength was fixed to 510
nm. Each plot was measured for three times and the average data was used.
0 mM
140
1 mM
2 mM
3 mM
120
4 mM
Emission Intensity
100
80
60
40
500 550 600
Wavelength (nm)
Figure S5. Stacked emission spectra of [tBu-Acr-Mes]+BF4- at different concentration of 1g.

S36
1.035
1.030
1.025
1.020
I0/I
1.015
1.010
KSV=7.629 M-1
1.005
R2=0.9955
1.000
0.000 0.002 0.004
[Q] / M
Figure S6. Stern-Volmer plot for the quenching study above, showing that alkyltrimethylgermanes is
able to be oxidized by the excited photocatalyst.
5 Crystal structure determination of 1n and 1o
5.1 Experimental procedure and crystal data of 1n.
Single crystals of C35 H58 GeO4 (1n) were grown by slow cooling of saturated MeOH/DCM solution
from 50 ℃ to room temperature. A suitable crystal was selected and intensity data was collected on a
'Bruker APEX-II CCD' diffractometer. The crystal was kept at 296.15 K during data collection. Using
Olex2[13], the structure was solved with the SHELXT[14] structure solution program using Intrinsic
Phasing and refined with the SHELXL[15] refinement package using Least Squares minimisation. Crystal
Data for C35H58 GeO4 (M =615.40 g/mol): monoclinic, space group P21 (no. 4), a = 6.4547(6) Å, b =
41.740(4) Å, c = 6.5720(6) Å, β = 105.666(2) , V = 1704.8(3) Å3, Z = 2, T = 296.15 K, μ(MoKα) =
0.932 mm-1, Dcalc = 1.199 g/cm3, 14046 reflections measured (3.904° ≤ 2Θ ≤ 55.018°), 7613
unique (Rint = 0.0250, Rsigma = 0.0638) which were used in all calculations. The final R1 was 0.0475 (I >
2σ(I)) and wR2 was 0.1098 (all data).
S37
Figure S7. X-ray Structure of compound 1n
Table 1 Crystal data and structure refinement for C35H58GeO4 (1n).
Identification code C35H58 GeO4
Empirical formula C35H58 GeO4
Formula weight 615.40
Temperature/K 296.15
Crystal system monoclinic
Space group P21
a/Å 6.4547(6)
b/Å 41.740(4)
c/Å 6.5720(6)
α/° 90
β/° 105.666(2)
γ/° 90
3
Volume/Å 1704.8(3)
Z 2
3
ρcalc g/cm 1.199
-1
μ/mm 0.932
F(000) 664.0
Crystal size/mm3 0.15 × 0.06 × 0.05
Radiation MoKα (λ = 0.71073)
2Θ range for data collection/° 3.904 to 55.018
Index ranges -6 ≤ h ≤ 8, -53 ≤ k ≤ 54, -8 ≤ l ≤ 8
S38
Reflections collected 14046
Independent reflections 7613 [Rint = 0.0250, Rsigma = 0.0638]
Data/restraints/parameters 7613/1/370
Goodness-of-fit on F2 1.059
Final R indexes [I>=2σ (I)] R1 = 0.0475, wR2 = 0.1064
Final R indexes [all data] R1 = 0.0558, wR2 = 0.1098
-3
Largest diff. peak/hole / e Å 0.46/-0.68
Flack parameter 0.065(6)
Table 2 Fractional Atomic Coordinates ( × 104) and Equivalent Isotropic Displacement

Parameters (Å2 ×103) for C35H58GeO4 (1n). Ueq is defined as 1/3 of the trace of the orthogonalised
UIJ tensor.
Atom x y z U(eq)
Ge1 7279.5(7) 2964.4(2) -256.0(7) 46.21(15)
O1 5041(7) 3959.8(10) 3099(8) 70.0(12)
O2 8524(10) 3984.3(17) 3515(15) 154(4)
O3 5488(6) 6268.2(8) 12820(6) 40.7(8)
O4 5115(6) 6752.1(8) 10921(5) 46.8(8)
C1 2921(10) 4785.9(13) 3465(8) 53.9(13)
C2 3004(11) 4443.2(14) 2689(9) 60.4(15)
C3 5013(10) 4284.2(13) 3893(10) 59.3(15)
C4 5135(10) 4273.7(13) 6248(10) 57.1(14)
C5 5021(9) 4607.9(13) 7083(10) 43.0(13)
C6 6480(8) 4709.4(13) 8763(9) 48.5(12)
C7 6563(8) 5039.8(12) 9702(8) 43.7(11)
C8 4498(8) 5230.1(12) 8884(9) 35.9(11)
C9 3589(7) 5178.0(10) 6461(7) 35.2(9)
C10 3147(7) 4821.0(12) 5851(7) 39.0(10)
C11 1662(9) 5398.5(12) 5466(8) 51.1(12)
C12 2065(9) 5752.9(12) 6084(8) 46.2(12)
C13 2804(7) 5793.2(10) 8469(7) 34.4(9)
C14 4844(6) 5586.3(11) 9284(7) 33.9(9)
C15 5870(9) 5716.6(13) 11511(9) 39.1(12)
C16 5726(7) 6077.6(11) 11075(7) 37.9(10)
C17 3675(7) 6132.6(11) 9212(7) 35.3(9)
C18 2340(7) 6363.5(12) 10175(7) 41.0(10)
C19 4065(7) 6523.2(11) 11932(7) 38.7(10)
C20 3279(9) 6682.0(12) 13657(8) 45.6(11)
C21 5048(9) 6866.4(13) 15194(9) 51.9(12)
S39
Parameters (Å2 ×103) for C35H58GeO4 (1n). Ueq is defined as 1/3 of the trace of the orthogonalised
UIJ tensor.
Atom x y z U(eq)
C22 6124(9) 7102.2(11) 14002(9) 48.5(12)
C23 6850(9) 6916.5(13) 12355(9) 52.5(13)
C24 7993(11) 7284.4(15) 15461(11) 69.7(17)
C25 866(10) 6589.7(15) 8586(9) 61.4(15)
C26 996(8) 5693.2(13) 9460(9) 50.2(13)
C27 1053(8) 4699.6(13) 6324(10) 53.1(13)
C28 6871(11) 3848.3(17) 2853(13) 76(2)
C29 6501(10) 3527.2(16) 1781(13) 75(2)
C30 8413(8) 3365.8(13) 1223(9) 49.4(12)
C31 9285(14) 3576.4(18) -274(13) 87(2)
C32 10196(13) 3295(2) 3195(13) 96(3)
C33 6232(14) 2685.0(19) 1587(13) 85(2)
C34 9542(12) 2736.7(19) -1133(13) 81(2)
C35 4953(11) 3068.5(17) -2754(11) 79(2)
Table 3 Anisotropic Displacement Parameters (Å2×103) for C35H58GeO4 (1n). The Anisotropic
displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].
Atom U11 U22 U33 U23 U13 U12
Ge1 42.7(3) 48.5(3) 45.8(3) -5.1(3) 9.01(18) 5.5(3)
O1 67(3) 49(2) 107(3) -32(2) 46(3) -14(2)
O2 80(4) 115(5) 283(10) -125(6) 76(5) -33(4)
O3 42.2(19) 34.1(18) 45(2) -3.9(14) 9.8(16) 4.4(15)
O4 55(2) 43.8(19) 49.6(19) 3.2(15) 27.9(16) -0.8(16)
C1 75(4) 46(3) 42(3) -3(2) 20(3) 3(3)
C2 80(4) 54(3) 50(3) -14(3) 21(3) -7(3)
C3 68(4) 41(3) 79(4) -19(3) 39(3) -11(3)
C4 64(4) 37(3) 71(4) -1(2) 19(3) 6(2)
C5 46(3) 36(3) 53(3) 2(2) 22(3) 6(2)
C6 41(3) 45(3) 61(3) 3(2) 17(3) 6(2)
C7 35(2) 43(3) 52(3) 0(2) 9(2) 3(2)
C8 32(3) 40(3) 39(3) 6(2) 14(2) 2(2)
C9 37(2) 33(2) 37(2) 1.4(17) 13.7(19) -3.5(18)
C10 41(2) 41(2) 36(2) -2.6(18) 13(2) -3(2)
C11 59(3) 43(3) 43(3) 0(2) 1(2) 5(2)
C12 53(3) 37(3) 43(3) 6(2) 4(2) 10(2)
C13 31(2) 33(2) 41(2) 4.4(18) 11.5(18) 4.1(17)
C14 25(2) 39(2) 39(2) 3.1(18) 10.7(17) -0.4(17)
S40
Table 3 Anisotropic Displacement Parameters (Å2×103) for C35H58GeO4 (1n). The Anisotropic
Atom U11 U22 U33 U23 U13 U12
C15 29(2) 37(3) 48(3) -3(2) 3(2) 5.4(19)
C16 34(2) 36(2) 46(3) -5.9(19) 15.0(19) -0.8(18)
C17 35(2) 36(2) 39(2) 6.0(18) 15.9(18) 2.8(18)
C18 35(2) 48(3) 42(3) 4(2) 14(2) 9(2)
C19 38(2) 43(3) 38(2) 6.0(19) 16(2) 3(2)
C20 54(3) 41(3) 49(3) 1(2) 26(2) 2(2)
C21 60(3) 49(3) 51(3) -3(2) 21(3) 1(2)
C22 51(3) 32(2) 61(3) 2(2) 12(2) 2(2)
C23 51(3) 47(3) 67(3) 2(2) 28(3) -4(2)
C24 70(4) 48(3) 84(4) -2(3) 8(3) -4(3)
C25 63(3) 62(4) 55(3) 2(3) 10(3) 27(3)
C26 37(3) 48(3) 73(4) 0(3) 26(3) -1(2)
C27 46(3) 45(3) 71(4) -3(3) 22(3) -12(2)
C28 56(4) 63(4) 114(6) -40(4) 33(4) -10(3)
C29 54(3) 64(4) 111(6) -38(4) 29(4) -1(3)
C30 43(3) 43(3) 62(3) -7(2) 14(2) 2(2)
C31 103(6) 65(4) 102(6) -10(4) 43(5) -18(4)
C32 86(5) 83(5) 92(6) -18(4) -25(4) 11(4)
C33 103(6) 74(5) 84(5) 0(4) 36(4) -5(4)
C34 75(4) 75(4) 104(5) -20(4) 42(4) 16(4)
C35 73(4) 79(5) 69(4) -5(3) -5(3) 6(3)
Table 4 Bond Lengths for C35H58GeO4 (1n).

Atom Atom Length/Å Atom Atom Length/Å
Ge1 C30 1.975(5) C9 C11 1.544(7)
Ge1 C33 1.930(8) C10 C27 1.552(7)
Ge1 C34 1.956(6) C11 C12 1.538(7)
Ge1 C35 1.951(6) C12 C13 1.519(6)
O1 C3 1.453(6) C13 C14 1.544(6)
O1 C28 1.320(8) C13 C17 1.554(6)
O2 C28 1.183(8) C13 C26 1.540(6)
O3 C16 1.438(6) C14 C15 1.534(7)
O3 C19 1.424(6) C15 C16 1.532(7)
O4 C19 1.434(6) C16 C17 1.559(6)
O4 C23 1.429(7) C17 C18 1.539(6)
C1 C2 1.524(8) C18 C19 1.524(7)
C1 C10 1.542(7) C18 C25 1.533(7)
S41
Table 4 Bond Lengths for C35H58GeO4 (1n).
C2 C3 1.481(9) C19 C20 1.514(7)
C3 C4 1.529(8) C20 C21 1.514(8)
C4 C5 1.508(8) C21 C22 1.536(8)
C5 C6 1.313(8) C22 C23 1.505(7)
C5 C10 1.543(7) C22 C24 1.526(8)
C6 C7 1.506(7) C28 C29 1.503(9)
C7 C8 1.520(7) C29 C30 1.535(8)
C8 C9 1.556(7) C30 C31 1.535(9)
C8 C14 1.516(7) C30 C32 1.512(9)
C9 C10 1.550(6)
Table 5 Bond Angles for C35H58GeO4 (1n).

Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚
C33 Ge1 C30 110.5(3) C26 C13 C14 112.0(4)
C33 Ge1 C34 107.9(4) C26 C13 C17 111.5(4)
C33 Ge1 C35 110.0(4) C8 C14 C13 114.6(4)
C34 Ge1 C30 110.5(3) C8 C14 C15 121.2(4)
C35 Ge1 C30 108.9(3) C15 C14 C13 103.9(4)
C35 Ge1 C34 109.1(3) C16 C15 C14 100.5(4)
C28 O1 C3 118.1(5) O3 C16 C15 114.1(4)
C19 O3 C16 106.4(4) O3 C16 C17 107.1(4)
C23 O4 C19 113.5(4) C15 C16 C17 106.7(4)
C2 C1 C10 115.3(5) C13 C17 C16 105.7(3)
C3 C2 C1 110.3(5) C18 C17 C13 120.3(4)
O1 C3 C2 108.7(5) C18 C17 C16 102.7(4)
O1 C3 C4 109.5(5) C19 C18 C17 102.1(4)
C2 C3 C4 110.6(5) C19 C18 C25 116.0(5)
C5 C4 C3 110.3(5) C25 C18 C17 114.8(4)
C4 C5 C10 116.8(5) O3 C19 O4 110.8(4)
C6 C5 C4 120.7(5) O3 C19 C18 104.0(4)
C6 C5 C10 122.6(5) O3 C19 C20 109.3(4)
C5 C6 C7 125.3(5) O4 C19 C18 106.3(4)
C6 C7 C8 113.8(4) O4 C19 C20 110.5(4)
C7 C8 C9 109.9(4) C20 C19 C18 115.8(4)
C14 C8 C7 112.2(4) C19 C20 C21 112.2(4)
C14 C8 C9 108.1(4) C20 C21 C22 110.4(4)
C10 C9 C8 113.0(4) C23 C22 C21 108.0(4)
C11 C9 C8 112.9(4) C23 C22 C24 111.2(5)
S42
Table 5 Bond Angles for C35H58GeO4 (1n).
C11 C9 C10 113.1(4) C24 C22 C21 112.9(5)
C1 C10 C5 108.9(4) O4 C23 C22 112.4(4)
C1 C10 C9 108.3(4) O1 C28 C29 109.7(5)
C1 C10 C27 108.9(4) O2 C28 O1 122.2(6)
C5 C10 C9 110.8(4) O2 C28 C29 127.9(6)
C5 C10 C27 108.0(4) C28 C29 C30 117.9(5)
C9 C10 C27 111.8(4) C29 C30 Ge1 106.0(4)
C12 C11 C9 113.7(4) C29 C30 C31 111.1(6)
C13 C12 C11 111.3(4) C31 C30 Ge1 108.8(4)
C12 C13 C14 107.3(4) C32 C30 Ge1 110.5(4)
C12 C13 C17 114.3(4) C32 C30 C29 110.8(6)
C12 C13 C26 110.1(4) C32 C30 C31 109.6(6)
C14 C13 C17 101.5(3)
Table 6 Torsion Angles for C35H58GeO4 (1n).

A B C D Angle/˚ A B C D Angle/˚
O1 C3 C4 C5 -177.8(5) C12 C13 C14 C15 163.0(4)
O1 C28 C29 C30 176.3(7) C12 C13 C17 C16 -137.4(4)
O2 C28 C29 C30 -7.7(15) C12 C13 C17 C18 107.1(5)
O3 C16 C17 C13 -128.1(4) C13 C14 C15 C16 -46.1(4)
O3 C16 C17 C18 -1.1(5) C13 C17 C18 C19 141.4(4)
O3 C19 C20 C21 69.6(5) C13 C17 C18 C25 -92.2(6)
O4 C19 C20 C21 -52.6(6) C14 C8 C9 C10 -179.5(4)
C1 C2 C3 O1 -179.6(5) C14 C8 C9 C11 -49.6(5)
C1 C2 C3 C4 60.2(6) C14 C13 C17 C16 -22.4(4)
C2 C1 C10 C5 45.7(6) C14 C13 C17 C18 -137.9(4)
C2 C1 C10 C9 166.3(5) C14 C15 C16 O3 149.3(4)
C2 C1 C10 C27 -71.8(6) C14 C15 C16 C17 31.2(5)
C2 C3 C4 C5 -58.1(7) C15 C16 C17 C13 -5.5(5)
C3 O1 C28 O2 10.5(13) C15 C16 C17 C18 121.5(4)
C3 O1 C28 C29 -173.2(6) C16 O3 C19 O4 -72.7(5)
C3 C4 C5 C6 -127.8(6) C16 O3 C19 C18 41.1(4)
C3 C4 C5 C10 51.3(7) C16 O3 C19 C20 165.3(4)
C4 C5 C6 C7 178.3(5) C16 C17 C18 C19 24.3(4)
C4 C5 C10 C1 -44.4(6) C16 C17 C18 C25 150.7(5)
C4 C5 C10 C9 -163.5(4) C17 C13 C14 C8 177.4(4)
C4 C5 C10 C27 73.8(6) C17 C13 C14 C15 42.8(4)
C5 C6 C7 C8 14.5(8) C17 C18 C19 O3 -40.5(4)
S43
Table 6 Torsion Angles for C35H58GeO4 (1n).
C6 C5 C10 C1 134.7(5) C17 C18 C19 O4 76.5(4)
C6 C5 C10 C9 15.6(7) C17 C18 C19 C20 -160.4(4)
C6 C5 C10 C27 -107.2(6) C18 C19 C20 C21 -173.4(4)
C6 C7 C8 C9 -41.3(6) C19 O3 C16 C15 -142.7(4)
C6 C7 C8 C14 -161.7(4) C19 O3 C16 C17 -24.8(5)
C7 C8 C9 C10 57.7(5) C19 O4 C23 C22 -60.4(5)
C7 C8 C9 C11 -172.3(4) C19 C20 C21 C22 53.0(6)
C7 C8 C14 C13 179.5(4) C20 C21 C22 C23 -54.0(6)
C7 C8 C14 C15 -54.6(6) C20 C21 C22 C24 -177.4(5)
C8 C9 C10 C1 -163.3(4) C21 C22 C23 O4 57.6(6)
C8 C9 C10 C5 -43.8(5) C23 O4 C19 O3 -65.4(5)
C8 C9 C10 C27 76.7(5) C23 O4 C19 C18 -177.8(4)
C8 C9 C11 C12 49.2(6) C23 O4 C19 C20 55.9(5)
C8 C14 C15 C16 -176.9(4) C24 C22 C23 O4 -178.0(4)
C9 C8 C14 C13 58.1(5) C25 C18 C19 O3 -166.0(4)
C9 C8 C14 C15 -176.0(4) C25 C18 C19 O4 -49.1(5)
C9 C11 C12 C13 -53.3(6) C25 C18 C19 C20 74.1(6)
C10 C1 C2 C3 -55.7(7) C26 C13 C14 C8 58.4(5)
C10 C5 C6 C7 -0.8(8) C26 C13 C14 C15 -76.1(5)
C10 C9 C11 C12 179.1(4) C26 C13 C17 C16 97.0(4)
C11 C9 C10 C1 66.9(5) C26 C13 C17 C18 -18.5(6)
C11 C9 C10 C5 -173.6(4) C28 O1 C3 C2 138.4(6)
C11 C9 C10 C27 -53.1(5) C28 O1 C3 C4 -100.7(7)
C11 C12 C13 C14 56.9(5) C28 C29 C30 Ge1 -177.5(6)
C11 C12 C13 C17 168.5(4) C28 C29 C30 C31 -59.6(9)
C11 C12 C13 C26 -65.2(5) C28 C29 C30 C32 62.5(9)
C12 C13 C14 C8 -62.5(5)
Table 7 Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement Parameters (Å2×103)
for C35H58GeO4 (1n).
Atom x y z U(eq)
H1A 1564.1 4880.74 2693.64 65
H1B 4062.55 4907.69 3122.78 65
H2A 1772.01 4324.56 2864.1 72
H2B 2940.51 4444.92 1197.36 72
H3 6253.94 4402.52 3691 71
H4A 3952.46 4146.7 6462.22 69
H4B 6470.82 4172.93 7017.26 69
S44
Atom x y z U(eq)
H6 7548.57 4565.5 9427.17 58
H7A 7738.76 5157.57 9394.61 52
H7B 6869.08 5020.67 11224.94 52
H8 3435.63 5154.34 9594.06 43
H9 4740 5244.18 5837.61 42
H11A 1323.57 5380.53 3939.66 61
H11B 418.67 5324.77 5895.81 61
H12A 3153.73 5838.08 5464 55
H12B 750.9 5873.74 5525.76 55
H14 5813.73 5651.85 8441.77 41
H15A 5057.34 5654.95 12493.68 47
H15B 7349.19 5646.34 12049.23 47
H16 7001.1 6148.26 10658.73 46
H17 4084.28 6241.06 8055.51 42
H18 1432.34 6234.31 10836.4 49
H20A 2719.9 6519.51 14421.79 55
H20B 2111.12 6827.31 13018.54 55
H21A 6114.12 6717.9 15997.79 62
H21B 4447.04 6983.22 16177.2 62
H22 5041.85 7258.43 13277.17 58
H23A 7508.47 7062.58 11565.2 63
H23B 7931.82 6761.95 13051.12 63
H24A 7534.07 7376.26 16606.56 105
H24B 8453.01 7451.84 14681.29 105
H24C 9166.11 7139.77 16013.67 105
H25A 1726.05 6741.88 8079.27 92
H25B -65.13 6701.24 9263.84 92
H25C 15.81 6467.74 7418.49 92
H26A 1530.23 5695.77 10971.96 75
H26B 515.19 5481.04 8997.23 75
H26C -184.68 5840.27 9027.93 75
H27A 1107.38 4744.6 7769.93 80
H27B 919.17 4472.75 6083.77 80
H27C -164.69 4806.4 5410.46 80
H29A 5356.26 3551.13 486.19 90
H29B 5981.5 3382.24 2687.33 90
H31A 10551.24 3479.08 -503.19 130
S45
Atom x y z U(eq)
H31B 9640.32 3784.41 344.92 130
H31C 8210.51 3597.33 -1599.55 130
H32A 9605.87 3190.07 4213.3 144
H32B 10870.41 3491.63 3779.43 144
H32C 11243.21 3157.72 2844.66 144
H33A 5211.8 2798.44 2143.14 127
H33B 7415.95 2615.81 2730.43 127
H33C 5548.42 2501.78 804.57 127
H34A 10739.44 2699.21 76.56 122
H34B 10004.84 2863.65 -2147.23 122
H34C 8994.19 2535.42 -1758.89 122
H35A 4551.86 2879.96 -3606.06 118
H35B 5427.29 3230.99 -3558.91 118
H35C 3734.08 3145.68 -2324.95 118
S46
5.2 Experimental procedure and crystal data of 1o.
Single crystals of C32H80 Ge4O4 (1o) were grown by vacuum sublimation at 3 mmHg, 40 ℃. A suitable
crystal was selected and intensity data was collected on a SuperNova, Dual, Cu at home/near,
AtlasS2 diffractometer. The crystal was kept at 150.00(10) K during data collection. Using Olex2[13], the
structure was solved with the SHELXT[14] structure solution program using Intrinsic Phasing and refined
with the SHELXL[15] refinement package using Least Squares minimisation. Crystal Data for
C32H80 Ge4O4 (M =819.32 g/mol): triclinic, space group P-1 (no. 2), a = 13.7154(13) Å, b =
13.7412(12) Å, c = 14.8757(14) Å, α = 78.696(7) ° , β = 63.721(9) ° , γ = 62.223(9) ° , V =
2224.0(4) Å3, Z = 2, T = 150.00(10) K, μ(Cu Kα) = 3.319 mm-1, Dcalc = 1.223 g/cm3, 13097 reflections
measured (7.272° ≤ 2Θ ≤ 146.226°), 8377 unique (Rint = 0.0677, Rsigma = 0.1230) which were used
in all calculations. The final R1 was 0.1013 (I > 2σ(I)) and wR2 was 0.2798 (all data).
Figure S8. X-ray Structure of compound 1o
Table 1 Crystal data and structure refinement for C8H20GeO (1o).

Identification code C8H20 GeO
Empirical formula C32H80 Ge4O4
Formula weight 819.32
Temperature/K 150.00(10)
Crystal system triclinic
Space group P-1
a/Å 13.7154(13)
S47
b/Å 13.7412(12)
c/Å 14.8757(14)
α/° 78.696(7)
β/° 63.721(9)
γ/° 62.223(9)
3
Volume/Å 2224.0(4)
Z 2
ρcalc g/cm3 1.223
-1
μ/mm 3.319
F(000) 864.0
3
Crystal size/mm 0.18 × 0.12 × 0.11
Radiation Cu Kα (λ = 1.54184)
2Θ range for data collection/° 7.272 to 146.226
Index ranges -14 ≤ h ≤ 17, -16 ≤ k ≤ 16, -18 ≤ l ≤ 18
Reflections collected 13097
Independent reflections 8377 [Rint = 0.0677, Rsigma = 0.1230]
Data/restraints/parameters 8377/38/389
2
Goodness-of-fit on F 1.077
Final R indexes [I>=2σ (I)] R1 = 0.1013, wR2 = 0.2434
Final R indexes [all data] R1 = 0.1424, wR2 = 0.2798
-3
Largest diff. peak/hole / e Å 3.76/-1.19

Parameters (Å2×103) for C8H20GeO (1o). Ueq is defined as 1/3 of of the trace of the orthogonalised
UIJ tensor.
Atom x y z U(eq)
Ge3 599.8(9) 8139.5(9) 1035.9(8) 42.9(3)
Ge1 8729.2(11) 1888.6(10) 3856.7(10) 49.8(3)
Ge2 2910.2(12) 2285.4(10) 4592.1(11) 55.3(4)
Ge4 6956.3(14) 7356.6(13) 720.5(13) 67.8(4)
O2 6121(6) 3079(6) 1434(5) 44.2(15)
O3 4424(5) 4476(6) 747(5) 48.2(16)
O1 5593(6) 5169(6) 5441(6) 55.5(18)
O4 5701(8) 4657(6) 2560(6) 61(2)
C20 2578(7) 6146(7) 1068(6) 33.9(18)
C17 1327(8) 6881(8) 1804(7) 41(2)
C19 1391(9) 7330(9) 2638(8) 54(3)
C21 3328(8) 5149(7) 1516(7) 43(2)
C4 7472(9) 4261(9) 4054(8) 49(2)
S48
Parameters (Å2×103) for C8H20GeO (1o). Ueq is defined as 1/3 of of the trace of the orthogonalised
UIJ tensor.
Atom x y z U(eq)
C1 8758(9) 3332(9) 3602(8) 51(2)
C12 4763(9) 2520(8) 2861(8) 52(2)
C23 651(10) 7599(10) -130(9) 61(3)
C5 6780(8) 4265(8) 5158(8) 47(2)
C18 525(9) 6264(9) 2280(9) 55(3)
C9 4206(9) 1701(8) 3273(9) 51(2)
C13 5866(9) 2184(9) 1911(9) 58(3)
C22 -1089(9) 9070(10) 1884(9) 68(3)
C24 1495(11) 9023(9) 540(9) 60(3)
C15 2091(13) 1338(12) 5143(10) 80(4)
C7 8592(11) 1373(10) 5201(9) 68(3)
C6 7393(13) 1945(11) 3623(12) 81(4)
C16 1793(11) 3786(10) 4447(11) 69(3)
C2 9544(10) 3411(11) 4022(12) 73(4)
C8 10267(13) 821(11) 2928(10) 88(5)
C3 9240(11) 3533(11) 2453(9) 71(4)
C10 3655(12) 1588(12) 2635(10) 76(4)
C14 3532(16) 2376(13) 5509(12) 93(5)
C11 5133(11) 550(10) 3391(13) 85(5)
C32 6810(20) 8826(14) 168(18) 143(9)
C27 4696(15) 7821(16) 767(14) 105(5)
C31 7810(17) 6299(17) -382(14) 140(9)
C26 4693(18) 8401(17) 2291(15) 122(7)
C28 5158(17) 6656(13) 2066(19) 161(9)
C29 6007(15) 5463(12) 2030(16) 125(7)
C30 7812(18) 6880(20) 1571(18) 150(10)
C25 5336(7) 7644(10) 1454(8) 87(4)
Table 3 Anisotropic Displacement Parameters (Å2 ×103) for C8H20GeO (1o). The Anisotropic
Atom U11 U22 U33 U23 U13 U12
Ge3 37.4(6) 38.1(6) 36.2(6) -2.1(4) -15.6(4) -1.7(4)
Ge1 54.2(7) 41.2(6) 50.6(7) -6.0(5) -26.6(6) -10.3(5)
Ge2 62.3(8) 47.2(7) 61.3(8) 13.2(6) -30.2(6) -27.2(6)
Ge4 67.7(9) 64.4(9) 76.4(11) 10.3(7) -26.1(8) -38.8(7)
O2 48(4) 51(4) 30(3) 8(3) -10(3) -27(3)
O3 31(3) 50(4) 45(4) -8(3) -14(3) -2(3)
S49
Table 3 Anisotropic Displacement Parameters (Å2 ×103) for C8H20GeO (1o). The Anisotropic
Atom U11 U22 U33 U23 U13 U12
O1 46(4) 53(4) 45(4) -11(3) -7(3) -10(3)
O4 93(6) 50(4) 45(4) 5(3) -26(4) -40(4)
C20 30(4) 35(4) 28(4) -3(3) -10(3) -7(3)
C17 33(4) 41(5) 35(5) -2(4) -11(4) -8(4)
C19 44(5) 59(6) 43(6) -14(5) -16(4) -7(5)
C21 33(4) 35(5) 33(5) -4(4) -4(4) 0(4)
C4 47(5) 51(6) 48(6) -10(5) -12(4) -23(5)
C1 42(5) 53(6) 48(6) -7(5) -11(5) -18(4)
C12 44(5) 44(5) 49(6) 4(4) -17(5) -10(4)
C23 56(6) 60(7) 51(7) -3(5) -26(5) -6(5)
C5 36(5) 44(5) 52(6) 0(4) -11(4) -16(4)
C18 42(5) 53(6) 54(6) 13(5) -16(5) -17(5)
C9 38(5) 45(5) 58(7) 11(5) -19(5) -13(4)
C13 47(6) 53(6) 70(8) 15(5) -29(5) -19(5)
C22 46(6) 60(7) 57(7) -3(6) -12(5) 2(5)
C24 71(7) 41(5) 50(7) -3(5) -16(6) -17(5)
C15 88(9) 80(9) 55(8) 12(7) -6(7) -49(8)
C7 67(7) 57(7) 50(7) -4(5) -21(6) -3(6)
C6 105(10) 69(8) 116(12) 6(8) -73(10) -48(8)
C16 70(8) 48(6) 75(9) -7(6) -24(7) -16(6)
C2 44(6) 65(8) 111(12) -19(7) -27(7) -21(5)
C8 108(11) 62(8) 50(7) -18(6) -26(7) -2(7)
C3 60(7) 72(8) 43(7) -2(6) -1(5) -17(6)
C10 80(9) 76(9) 58(8) -2(7) -21(7) -27(7)
C14 135(14) 88(11) 84(11) 18(8) -67(11) -55(10)
C11 56(7) 46(6) 126(13) 31(7) -33(8) -16(5)
C32 210(20) 72(11) 180(20) 55(13) -93(19) -96(14)
C27 100(8) 110(9) 109(9) 8(7) -43(7) -48(7)
C31 133(15) 146(17) 95(13) -65(13) 57(12) -94(14)
C26 124(10) 114(10) 117(10) -10(8) -29(7) -57(8)
C28 106(12) 153(14) 177(17) 19(12) -56(12) -28(11)
C29 100(10) 71(9) 157(15) 27(9) -8(10) -51(8)
C30 137(16) 220(30) 190(20) 101(19) -133(17) -119(18)
C25 75(6) 84(7) 77(7) -39(5) -61(6) 30(5)
S50
Table 4 Bond Lengths for C8H20GeO (1o).
Ge3 C17 1.980(9) O1 C5 1.443(11)
Ge3 C23 1.978(11) O4 C29 1.351(16)
Ge3 C22 1.969(10) C20 C17 1.523(11)
Ge3 C24 1.940(12) C20 C21 1.521(12)
Ge1 C1 1.960(11) C17 C19 1.540(13)
Ge1 C7 1.942(12) C17 C18 1.541(14)
Ge1 C6 1.977(12) C4 C1 1.543(13)
Ge1 C8 1.960(12) C4 C5 1.489(14)
Ge2 C9 1.963(11) C1 C2 1.515(15)
Ge2 C15 1.939(13) C1 C3 1.555(16)
Ge2 C16 1.955(12) C12 C9 1.531(15)
Ge2 C14 1.949(14) C12 C13 1.487(15)
Ge4 C32 1.977(15) C9 C10 1.516(17)
Ge4 C31 1.955(15) C9 C11 1.537(14)
Ge4 C30 1.917(15) C27 C25 1.541(19)
Ge4 C25 1.868(8) C26 C25 1.45(2)
O2 C13 1.406(12) C28 C29 1.498(9)
O3 C21 1.420(10) C28 C25 1.535(10)
Table 5 Bond Angles for C8H20GeO (1o).

C23 Ge3 C17 110.0(4) C19 C17 Ge3 108.5(7)
C22 Ge3 C17 110.6(4) C19 C17 C18 109.4(9)
C22 Ge3 C23 108.9(5) C18 C17 Ge3 109.0(6)
C24 Ge3 C17 110.2(5) O3 C21 C20 110.5(7)
C24 Ge3 C23 108.1(5) C5 C4 C1 117.6(9)
C24 Ge3 C22 109.0(5) C4 C1 Ge1 110.8(7)
C1 Ge1 C6 109.9(5) C4 C1 C3 105.9(9)
C7 Ge1 C1 112.6(5) C2 C1 Ge1 111.4(8)
C7 Ge1 C6 110.1(6) C2 C1 C4 109.6(9)
C7 Ge1 C8 106.6(5) C2 C1 C3 109.5(10)
C8 Ge1 C1 108.0(6) C3 C1 Ge1 109.4(8)
C8 Ge1 C6 109.5(7) C13 C12 C9 115.6(9)
C15 Ge2 C9 108.8(5) O1 C5 C4 109.9(9)
C15 Ge2 C16 110.9(6) C12 C9 Ge2 105.8(7)
C15 Ge2 C14 109.8(7) C12 C9 C11 111.8(9)
C16 Ge2 C9 109.4(5) C10 C9 Ge2 107.9(7)
C14 Ge2 C9 111.6(6) C10 C9 C12 113.6(10)
S51
Table 5 Bond Angles for C8H20GeO (1o).
C14 Ge2 C16 106.4(6) C10 C9 C11 108.0(11)
C31 Ge4 C32 109.3(10) C11 C9 Ge2 109.6(9)
C30 Ge4 C32 111.3(9) O2 C13 C12 112.0(9)
C30 Ge4 C31 109.4(11) C29 C28 C25 132.0(15)
C25 Ge4 C32 100.8(8) O4 C29 C28 125.7(14)
C25 Ge4 C31 114.3(7) C27 C25 Ge4 111.9(9)
C25 Ge4 C30 111.4(7) C26 C25 Ge4 115.4(11)
C21 C20 C17 115.8(7) C26 C25 C27 116.8(13)
C20 C17 Ge3 107.0(6) C26 C25 C28 96.7(14)
C20 C17 C19 111.5(7) C28 C25 Ge4 113.1(10)
C20 C17 C18 111.3(8) C28 C25 C27 100.9(14)
Table 6 Torsion Angles for C8H20GeO (1o).

C17 C20 C21 O3 174.6(8) C32 Ge4 C25 C26 -64.5(14)
C21 C20 C17 Ge3 177.1(7) C32 Ge4 C25 C28 -174.6(15)
C21 C20 C17 C19 58.6(11) C31 Ge4 C25 C27 -44.8(14)
C21 C20 C17 C18 -63.9(11) C31 Ge4 C25 C26 178.4(14)
C1 C4 C5 O1 -178.4(8) C31 Ge4 C25 C28 68.3(16)
C5 C4 C1 Ge1 60.8(11) C29 C28 C25 Ge4 -14(3)
C5 C4 C1 C2 -62.6(13) C29 C28 C25 C27 105(3)
C5 C4 C1 C3 179.3(10) C29 C28 C25 C26 -135(3)
C9 C12 C13 O2 163.0(9) C30 Ge4 C25 C27 -169.5(12)
C13 C12 C9 Ge2 173.2(8) C30 Ge4 C25 C26 53.7(16)
C13 C12 C9 C10 -68.6(12) C30 Ge4 C25 C28 -56.4(17)
C13 C12 C9 C11 54.0(14) C25 C28 C29 O4 -174(2)
C32 Ge4 C25 C27 72.3(13)
for C8H20GeO (1o).
Atom x y z U(eq)
H3 4931 4081 992 72
H1 5193 5146 6060 83
H20A 2489 5885 546 41
H20B 3030 6597 732 41
H19A 1901 7722 2336 80
H19B 1735 6717 3035 80
H19C 579 7835 3074 80
H21A 3507 5395 1983 52
S52
for C8H20GeO (1o).
Atom x y z U(eq)
H21B 2865 4716 1900 52
H4A 7527 4972 3876 59
H4B 6999 4230 3724 59
H12A 4148 3229 2752 62
H12B 4963 2649 3377 62
H23A 1488 7254 -619 92
H23B 175 8218 -441 92
H23C 317 7058 93 92
H5A 6710 3562 5359 57
H5B 7210 4338 5509 57
H18A -301 6780 2682 82
H18B 839 5681 2711 82
H18C 525 5939 1750 82
H13A 6559 1621 2056 70
H13B 5756 1848 1452 70
H22A -1506 8605 2250 102
H22B -1489 9580 1462 102
H22C -1114 9488 2363 102
H24A 1554 9235 1099 90
H24B 1078 9686 225 90
H24C 2306 8595 45 90
H15A 1958 1146 4619 120
H15B 1313 1723 5695 120
H15C 2587 665 5395 120
H7A 9005 1638 5418 102
H7B 8962 567 5201 102
H7C 7739 1653 5662 102
H6A 6621 2423 4130 122
H6B 7445 1202 3668 122
H6C 7450 2237 2954 122
H16A 2147 4290 4367 104
H16B 1033 3998 5045 104
H16C 1638 3822 3855 104
H2A 9195 3356 4754 110
H2B 9590 4118 3838 110
H2C 10355 2810 3745 110
H8A 10347 1019 2237 132
S53
for C8H20GeO (1o).
Atom x y z U(eq)
H8B 10291 85 3065 132
H8C 10932 825 3016 132
H3A 10058 2958 2124 107
H3B 9256 4254 2325 107
H3C 8712 3513 2187 107
H10A 3268 1093 2963 114
H10B 4287 1287 1975 114
H10C 3052 2313 2557 114
H14A 4202 1668 5514 140
H14B 2890 2552 6187 140
H14C 3817 2952 5289 140
H11A 5449 592 3851 127
H11B 5796 272 2736 127
H11C 4743 50 3663 127
H32A 7609 8790 -254 214
H32B 6401 9353 719 214
H32C 6331 9064 -235 214
H27A 4609 8520 417 158
H27B 3898 7838 1172 158
H27C 5175 7217 275 158
H31A 7302 6463 -742 210
H31B 7994 5554 -114 210
H31C 8561 6350 -843 210
H26A 5146 8162 2712 183
H26B 3895 8414 2688 183
H26C 4603 9139 2040 183
H28A 4832 6882 2772 193
H28B 4481 6655 1983 193
H29A 6404 5234 1317 150
H29B 6641 5434 2200 150
H30A 8632 6814 1178 225
H30B 7847 6161 1852 225
H30C 7393 7415 2116 225
H4 5910(130) 4150(90) 2180(90) 105
H2 6815(9) 2872(15) 957(11) 105
S54
6 Reference
1. S. M. Khake, S. Jain, U. N. Patel, R. G. Gonnade, K. Vanka, B. Punji, Organometallics 2018, 37,

2037-2045.
2. A. C. Spivey, C. M. Diaper, A. J. Rudge, Chem. Commun. 1999, 835-836.
3. K. Seizi, T. Shoji, Y. Tetsuya, Y. Shigeru, T. Waichiro, Bull. Chem. Soc. Jpn. 1985, 58, 3277-3281.
4. E. Shim, A. Zakarian, Synlett 2020, 31, 683-686.
5. J. D. Pelletier, D. Poirier, Tetrahedron Lett. 1994, 35, 1051-1054.
6. J. Wang, M. Shang, H. Lundberg, K. S. Feu, S. J. Hecker, T. Qin, D. G. Blackmond, P. S. Baran,
ACS Catal. 2018, 8, 9537-9542.
7. X.-Y. Zhang, W.-Z. Weng, H. Liang, H. Yang, B. Zhang, Org. Lett. 2018, 20, 4686-4690.
8. D. Kruger, A. E. Sopchik, C. A. Kingsbury, J. Org. Chem. 1984, 49, 778-788.
9. Q.-K. Zhao, X. Wu, F. Yang, P.-C. Yan, J.-H. Xie, Q.-L. Zhou, Org. Lett. 2021, 23, 3593-3598.
10. M. Uno, S. Sumino, T. Fukuyama, M. Matsuura, Y. Kuroki, Y. Kishikawa, I. Ryu, J. Org. Chem.
2019, 84, 9330-9338.
11. D. Mazzarella, A. Pulcinella, L. Bovy, R. Broersma, T. Noël, Angew. Chem. Int. Ed. 2021, 60, 21277-
21282; Angew. Chem. 2021, 133, 21447-21452.
12. L. Whitaker, H. Y. Harb, A. P. Pulis, Chem. Commun. 2017, 53, 9364-9367.
13. O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. Howard, H. Puschmann, J. Appl. Crystallogr.
2009, 42, 339-341.
14. G. M. Sheldrick, Acta Cryst. Sec. A 2015, 71, 3-8.
15. G. M. Sheldrick, Acta Cryst. Sec. C 2015, 71, 3-8.
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7 NMR spectra
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CT BR2618-2 Si

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Supporting Information

Alkyl-GeMe3: Neutral Metalloid Radical Precursors upon Visible-

1. General information .......................................................................................................2

1.1 Reagent information

1.2 Analytical information

Figure S1. Photocatalytic reaction set-up.

Table S1. Screening of the photocatalysts.

3.1 Preparation and characterization of alkyltrimethylgermane

3-methyl-3-(trimethylgermyl)butanoic acid (1m)

3-methyl-3-(trimethylgermyl)butanoic acid diosgenin ester (1n)

5,5-dicyano-3,3-dimethyl-4-phenylpentanoic acid (3m)

2-benzyl-3-cyclohexylpropanoic acid (3r)

dimethyl 2-cyclohexylsuccinate (3s)

ethyl 3-cyclohexyl-2-phenylpropanoate (3u)

Ethyl 4-cyclohexyl-2-oxochromane-3-carboxylate (3x)

5-(methoxycarbonyl)-3,3-dimethylhex-5-enoic acid diosgenin ester (3y)

Methyl 2-methylene-4-phenylbutanoate (3z)

Methyl 2-(cyclohexylmethyl)acrylate (3aa)

Methyl 2-((1-butylcyclohexyl)methyl)acrylate (3ab)

3.3 General procedure of Ni catalyzed photoredox cross-coupling reaction and characterization of

Methyl 4-cyclohexylbenzoate (4c)

Methyl 2-cyclohexylbenzoate (4k)

Methyl 4-benzylbenzoate (4p)

Methyl 2-benzylbenzoate (4s)

4.2 Competitive radical addition using 5

Figure S4. Cyclic voltammogram of cyclohexyltrimethylgermane 1a, [0.01 M] in [0.1 M] TBAPF 6 in

4.4 Stern-Volmer Fluorescence Quenching Studies

Solutions with [tBu-Acr-Mes]+BF4- concentration at 0.01 mM and different concentrations of 1g in

Figure S5. Stacked emission spectra of [tBu-Acr-Mes]+BF4- at different concentration of 1g.

5 Crystal structure determination of 1n and 1o

5.1 Experimental procedure and crystal data of 1n.

Table 2 Fractional Atomic Coordinates ( × 104) and Equivalent Isotropic Displacement

Table 4 Bond Lengths for C35H58GeO4 (1n).

Table 5 Bond Angles for C35H58GeO4 (1n).

Table 6 Torsion Angles for C35H58GeO4 (1n).

Figure S8. X-ray Structure of compound 1o

Table 1 Crystal data and structure refinement for C8H20GeO (1o).

Table 2 Fractional Atomic Coordinates ( × 104) and Equivalent Isotropic Displacement

Table 5 Bond Angles for C8H20GeO (1o).

Table 6 Torsion Angles for C8H20GeO (1o).

1. S. M. Khake, S. Jain, U. N. Patel, R. G. Gonnade, K. Vanka, B. Punji, Organometallics 2018, 37,

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