Supporting Information

Cooperative Ligand-Promoted P(III)-Directed

Ruthenium-Catalyzed Remote meta-C–H Alkylation of Tertiary
Phosphines

Zheng-Xin Zhou,† Jia-Wei Li,† Liang-Neng Wang,† Ming Li,† Yue-Jin Liu,*,† and Ming-Hua Zeng*,†,‡

†
Collaborative Innovation Center for Advanced Organic Chemical Materials Co-constructed by the
Province and Ministry, Ministry of Education Key Laboratory for the Synthesis and Application of
Organic Functional Molecules. College of Chemistry and Chemical Engineering, Hubei University,
Wuhan 430062, P. R. China.

‡
Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, School of
Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin, 541004, P. R. China.

Table of Contents

1. General Information ............................................................................................................................. S2

2. Experimental Procedures ...................................................................................................................... S2
2.1 Optimization studies ....................................................................................................................... S2
2.2 General procedure for meta-selective C–H alkylation of tertiary phosphines ............................... S4
2.3 Synthetic application ...................................................................................................................... S4
2.4 Mechanism studies ......................................................................................................................... S6
2.5 Proposed catalytic cycle ............................................................................................................... S10
3. Characterization data .......................................................................................................................... S10
4. References .......................................................................................................................................... S35
5. NMR spectra ...................................................................................................................................... S35

S1
1. General Information

Unless otherwise noted, all reactions were carried out in a flame dried sealed Schlenk reaction tube
under an atmosphere of argon in an oil bath. Materials were purchased from Alfa-Aesar and J&K
Scientific Ltd. and used as received. All the solvents were purchased from commercial suppliers
without further purification. Analytical thin layer chromatography (TLC) was performed on silica gel
plates with F-254 indicator and compounds were visualized by irradiation with UV light. Flash column
chromatography was carried out using silica gel (200-300 mesh) at increased pressure. The 1H, 13C, 31P
and 19F NMR spectroscopic data were recorded on Bruker Mercury Plus 400 MHz NMR spectrometers.
Chemical shifts (δ) for 1H and 13C are referenced to internal solvent resonances and reported relative to
SiMe4. 1H NMR coupling constants were reported in Hz, and multiplicity was indicated as follows: s
(singlet); d (doublet); t (triplet); q (quartet); m (multiplet); dd (doublet of doublets); dt (doublet of
triplets); td (triplet of doublets). High resolution mass spectra (HRMS) were recorded on the Thermo
Scientific Exactive Plus (orbitrap) equipped with ESI ionization source.

2. Experimental procedures

2.1 Optimization studies

Table S1: Influence of the solvent

S2
Table S2: Influence of the ligand

S3
Table S3: Influence of the base

2.2 General procedure for meta-selective C–H alkylation of tertiary phosphines

Scheme S1:

Scheme S1
A mixture of phosphines (0.3 mmol, 1.0 equiv), alkylating reagents (0.9 mmol, 3.0 equiv),
[RuCl2(p-cymene)]2 (9.2mg, 5.0 mol%), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 30 mol%),
KOAc (58.8mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24
h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture
was filtered through a short pad of silica gel. The solvent was removed in vacuo and the residue was
purified by prepared column chromatography.

2.3 Synthetic application

a) Gram-scale reaction
Scheme S2:

A mixture of 2-diphenylphosphinobiphenyl 1a (1.0 g, 2.96 mmol, 1.0 equiv), ethyl bromopropionate 2a

(1.60 g, 8.88 mmol, 3.0 equiv), [RuCl2(p-cymene)]2 (90.6 mg, 5.0 mol%),
2,2,6,6-tetramethylheptane-3,5-dione (163.4 mg, 0.888 mmol, 30 mol %), KOAc (580.2 mg, 5.92 mmol,

S4
2.0 equiv) in toluene (30.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, the mixture was filtered through a short pad of silica gel. The solvent
was removed in vacuo and the residue was purified by prepared column chromatography (PE/EA=50:1)
on silica gel to afford the pure products 3a (552.1 mg, 43%) and 3a’ (478.3 mg, 30%).
b) Evaluation of meta-substituted phosphine ligand in Pd catalyzed Suzuki coupling
Scheme S3:

A mixture of 1-chloro-4-methylbenzene 5 (126 mg, 1.0 mmol, 1.0 equiv), phenylboronic acid 6 (146.4
mg, 1.2 mmol, 1.2 equiv), Pd(OAc)2 (2.24 mg, 0.01 mmol), ligand (0.02 mmol), KF (115.9 mg, 2.0
mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 100℃ in heating mantle for 12 h under an
atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered
through a short pad of silica gel. The solvent was removed in vacuo and the residue was purified by
prepared column chromatography to afford product 7 (4-methyl-1,1'-biphenyl) [1] as white solid. 1H
NMR (400 MHz, CDCl3) δ 7.56 (d, J = 8.0 Hz, 2H), 7.48 (d, J = 8.0 Hz, 2H), 7.41 (t, J = 8.0 Hz, 2H),
7.30 (t, J = 8.0 Hz, 1H), 7.23 (d, J = 8.0 Hz, 2H), 2.38 (s, 3H).

c) Synthesis of multifunctional phosphines

Scheme S4:

S5
A mixture of 2-diphenylphosphinobiphenyl 3a (67.6 mg, 0.2 mmol, 1.0 equiv), ethyl acrylate (60.0 mg,
0.6 mmol, 3.0 equiv), [RuCl2(p-cymene)]2 (6.1 mg, 0.01 mmol), N-Boc-L-Phe-OH (15.9 mg, 0.06
mmol), K2HPO4 (69.6 mg, 0.4 mmol, 2.0 equiv). The tube was purged with Ar three times, followed by
addition of n-hexane (1 mL). The mixture was stirred at 120 °C in an oil bath for 12 h. At ambient
temperature, the mixture was filtered through a short pad of silica gel. The solvent was removed in
vacuo and the residue was purified by prepared column chromatography (Rf = 0.4, PE/EA=10:1) on
silica gel to afford the pure products 8 (pale yellow oil, 77.6 mg, 72%).[2]
Scheme S5:

A mixture of 2-diphenylphosphinobiphenyl 3a (67.6 mg, 0.2 mmol, 1.0 equiv), 2-iodoanisole (70.2 mg,
0.3 mmol, 1.5 equiv), [RuCl2(p-cymene)]2 (6.1mg, 5.0 mol%), N-Ac-L-Ala-OH (7.9mg, 30 mol%),
CsOAc (76.8mg, 0.4 mmol, 2.0 equiv). The tube was purged with Ar three times, followed by addition
of toluene (2 mL). The mixture was stirred at 160 °C for 12 h. At ambient temperature, the mixture was
filtered through a short pad of silica gel. The solvent was removed in vacuo and the residue was purified
by prepared column chromatography (Rf = 0.6, PE/EA=10:1) on silica gel to afford the pure products 9
(pale yellow oil, 87.2 mg, 80%).[3]

2.4 Mechanism studies

Table S4: Radical trapping experiment

S6
A mixture of 2-diphenylphosphinobiphenyl 1a (101.4 mg, 0.3 mmol, 1.0 equiv), ethyl bromopropionate
2a (162.0 mg, 0.9 mmol, 3.0 equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol),
2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 30 mol%), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in
toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of argon. At
ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short pad of
silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (PE/EA = 20/1) to afford product 3a and compound 10. The compound 11 was
detected by HRMS.

1
H NMR (400 MHz, CDCl3) δ 7.41-7.33 (m, 3H), 7.26-7.21 (m, 6H), 7.20 (d, J = 1.2 Hz, 1H), 6.12 (d, J
= 12.0 Hz, 1H), 4.14 (q, J = 7.2 Hz, 2H), 3.26 (m, 1H), 1.26 (dd, J = 8.0, 7.2 Hz, 6H).
Synthesis of ruthenium(II) Int A[1]
Scheme S6:

S7
To a 50 mL Schlenk flask was added 2-diphenylphosphinobiphenyl 1a (676.0 mg, 2 mmol, 1.0 equiv),
[RuCl2(p-cymene)]2 (612.0 mg, 1 mmol), KOAc (490.0 mg, 5 mmol, 2.0 equiv). The tube was purged
with Ar three times, followed by addition of 30 mL DCM. The mixture was stirred at rt in an oil bath
for 24 h. The solvent was then removed under vacuum directly. The crude product was purified by
neutral alumina (Al2O3) column chromatography (Rf = 0.4, EA/hexane = 5/1) to afford the product as
red powder (860.2 mg, 71% yield). 1H NMR (400 MHz, CDCl3) δ 8.18 -8.11 (m, 1H), 8.05-7.95 (m,
2H), 7.72 (dd, J = 7.6, 4.0 Hz, 1H), 7.64 (t, J = 8.0 Hz, 1H), 7.56-7.46 (m, 3H), 7.42 (t, J = 7.6 Hz, 1H),
7.32-7.14 (m, 4H), 6.96 (t, J = 7.2 Hz, 1H), 6.92-6.81 (m, 4H), 5.15 (d, J = 5.6 Hz, 1H), 5.06 (d, J = 6.0
Hz, 1H), 4.82 (d, J = 6.4 Hz, 1H), 4.34 (d, J = 6.0 Hz, 1H), 2.50 (dt, J = 13.8, 6.8 Hz, 1H), 1.34 (s, 3H),
1.11 (d, J = 6.8 Hz, 3H), 0.95 (d, J = 6.8 Hz, 3H).The analytical data are in accordance with those
reported in the literature.[1]
Int A as the catalyst
Scheme S7:

A mixture of 2-diphenylphosphinobiphenyl 1a (33.8 mg, 0.1 mmol, 1.0 equiv), ethyl bromopropionate
2a (54.0 mg, 0.3 mmol, 3.0 equiv), Int A (6.1 mg, 0.01 mmol), 2,2,6,6-tetramethylheptane-3,5-dione
(5.5 mg, 0.03 mmol), KOAc (19. 6mg, 0.2 mmol, 2.0 equiv) in toluene (1.0 mL) was stirred at 140℃ in
heating mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was
added, and the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo
and the residue was purified by prepared column chromatography to afford the 3a in 80% yield in the
presence of ligand (30 mol%) or 30% yield in the absence of ligand, respectively.
Int A as the substrate
Scheme S8:

A mixture of Int A (61.4 mg, 0.1 mmol, 1.0 equiv), ethyl bromopropionate 2a (54.0 mg, 0.3 mmol, 3.0

S8
equiv), 2,2,6,6-tetramethylheptane-3,5-dione (18.4 mg, 0.1 mmol, 1.0 equiv), MesCO2H (16.4 mg, 0.1
mmol, 1.0 equiv), KOAc (19.6 mg, 0.2 mmol, 2.0 equiv) in toluene (1.0 mL) was stirred at 140℃ in
heating mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was
added, and the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo
and the residue was purified by prepared column chromatography to afford the 3a in 20% yield.

H/D exchange experiment

Scheme S9:

A mixture of 2-diphenylphosphinobiphenyl 1a (33.8mg, 0.1 mmol, 1.0 equiv), ethyl bromopropionate

2a (54.0mg, 0.3 mmol, 3.0 equiv), [RuCl2(p-cymene)]2 (3.1mg, 5.0 mol%), CD3OD (36.1mg, 1.0 mmol,
10.0 equiv), 2,2,6,6-tetramethylheptane-3,5-dione (5.5mg, 30 mol%), KOAc (19.6mg, 0.2 mmol, 2.0
equiv) in toluene (1.0 mL) was stirred at 140℃ in heating mantle for 1 h under an atmosphere of argon.
At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short pad of
silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography to afford the mixture products D-3a in 36% yield, which was analyzed by 1H NMR
spectroscopy.

69% D

26% D

S9
KIE experiment
Scheme S10:

A mixture of 2-diphenylphosphinobiphenyl 1a (16.9 mg, 0.05 mmol, 0.5 equiv), D5-1a (17.2 mg, 0.05
mmol, 0.5 equiv),ethyl bromopropionate 2a (54.0 mg, 0.3 mmol, 3.0 equiv), [RuCl2(p-cymene)]2 (3.1
mg, 0.005 mmol), CD3OD (36.1 mg, 1.0 mmol, 10.0 equiv), 2,2,6,6-tetramethylheptane-3,5-dione (5.5
mg, 0.03 mmol), KOAc (19.6 mg, 0.2 mmol, 2.0 equiv) in toluene (1.0 mL) was stirred at 140℃ in
heating mantle for 4 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was
added, and the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo
and the residue was purified by prepared column chromatography to afford the mixture products
(3a:D4-3a = 4.6:1), which was analyzed by 1H NMR spectroscopy.

2.5 Proposed catalytic cycle

Scheme S11:

First, an active ruthenium species I generates from [RuCl2(p-cymene)]2 in the presence of ligand (L6)
and KOAc. Then, the Ru species I coordinates with substrate 1a, to afford intermediat II which forms

S10
the six-membered cycloruthenated complex III via ortho-C–H bond ruthenation of 1a. Next, the alkyl
radical generated in situ attacks the para-position of C–Ru bond in complex III to form meta-alkylated
intermediate IV, which converts into ruthenium complex V via protonation reaction. Finally, the
complex V delivers the product 3a and the active ruthenium catalyst I.

3. Characterization data

ethyl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (3a)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and
the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the
residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the
title compound as colorless oil (122.2 mg, 93% yield). 1H NMR (400 MHz, CDCl3) δ 7.38 (t, J = 8.0
Hz, 1H), 7.33-7.27 (m, 8H), 7.24-7.19 (m, 6H), 7.15-7.13 (m, 1H), 7.06-7.02 (m, 2H), 4.15-4.02 (m,
2H), 3.53 (q, J = 8.0 Hz, 1H), 1.32 (d, J = 8.0 Hz, 3H), 1.19 (t, J = 8.0 Hz, 3H). 13C NMR (100 MHz,
CDCl3) δ 174.5, 148.0 (d, J = 28.0 Hz), 141.9 (d, J = 6.0 Hz), 139.8, 137.8 (d, J = 12.0 Hz), 137.6 (d, J
= 12.0 Hz), 135.9 (d, J = 14.0 Hz), 134.0 (d, J = 19.0 Hz), 130.1 (d, J = 4.0 Hz), 129.2 (d, J = 4.0 Hz),
128.5 (d, J = 2.0 Hz), 128.43 (d, J = 1.0 Hz), 128.37 (d, J = 1.0 Hz), 128.3 (d, J = 4.0 Hz), 127.9, 127.4,
126.3, 60.7, 45.4, 18.3, 14.2. 31P NMR (162 MHz, CDCl3) δ -13.1. HRMS (ESI) m/z: [M+H]+ calcd for
C29H28O2P 439.1821; found 439.1823.

diethyl 2,2'-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3,5-diyl)dipropanoate (3a’)

The general procedure was applied to 1a (1.0 g, 2.96 mmol, 1.0 equiv), 2a (1.60 g, 8.88 mmol, 3.0
equiv), [RuCl2(p-cymene)]2 (90.6 mg, 0.05 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (163.4 mg,
0.888 mmol), KOAc (580.2 mg, 5.92 mmol, 2.0 equiv) in toluene (10 mL) was stirred at 140℃ in
heating mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was
added, and the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo

S11
and the residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to
afford the title compound as colorless oil (478 mg, 30% yield). 1H NMR (400 MHz, CDCl3) δ 7.37 (t, J
=8.0 Hz, 1H), 7.33-7.26 (m, 7H), 7.23-7.15 (m, 5H), 7.12 (s, 1H), 7.05-7.00 (m, 3H), 4.14-4.05 (m, 4H),
3.56 (q, J = 8.0 Hz, 2H), 1.35 (d, J = 8.0 Hz, 6H), 1.20 (t, J = 8.0 Hz, 6H). 13C NMR (100 MHz, CDCl3)
δ 174.4, 147.7 (d, J = 28.0 Hz), 142.1 (d, J = 6.0 Hz), 140.0 (d, J = 2.0 Hz), 137.8, 137.7, 137.6, 137.4,
136.1, 135.9, 134.1, 134.0, 133.9, 130.2 (d, J = 4.0 Hz), 128.6, 128.5, 128.4 (d, J = 7.0 Hz), 127.7 (d, J
= 2.0 Hz), 127.4, 125.6 (d, J = 4.0 Hz), 60.7, 45.4 (d, J = 1.0 Hz), 18.3 (d, J = 3.0 Hz), 14.2. 31P NMR
(162 MHz, CDCl3) δ -12.5. HRMS (ESI) m/z: [M+H]+ calcd for C34H36O4P 539.2346; found 539.2341.

ethyl 2-(2'-(diphenylphosphino)-5'-fluoro-[1,1'-biphenyl]-3-yl)propanoate (3b)

The general procedure was applied to 1b (106.9 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and
the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the
residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the
title compound as colorless oil (113.5 mg, 83% yield). 1H NMR (400 MHz, CDCl3) δ 7.34-7.27 (m,
2H), 7.24 (dd, J = 4.0, 1.2 Hz, 1H), 7.23-7.16 (m, 1H), 7.14-7.10 (m, 1H), 7.08-7.03 (m, 1H), 7.02-6.93
(m, 1H), 4.09-4.02 (m, 2H), 3.53 (q, J = 7.2 Hz, 1H), 1.32 (d, J = 7.2 Hz, 3H), 1.19 (t, J = 7.2 Hz, 3H).
13C NMR (100 MHz, CDCl3) δ 174.4, 163.0 (d, 1JC-F = 250.0 Hz), 150.4 (d, J = 8.0 Hz), 150.1 (d, J =
8.0 Hz), 140.9 (dd, J = 6.0, 2.0 Hz), 140.0, 137.7 (d, 3JC-F = 12.0 Hz), 137.5 (d, 3JC-F= 12.0 Hz), 136.2
(d, J = 8.0 Hz), 133.8 (d, 2JC-F= 20.0 Hz), 131.5 (d, J = 3.0 Hz), 131.4 (d, J = 3.0 Hz), 128.9 (d, J = 4.0
Hz), 128.6 (d, J = 2.0 Hz), 128.5 (d, J = 1.0 Hz), 128.4 (d, J = 1.0 Hz), 128.1 (d, J = 3.0 Hz), 128.0,
126.8, 117.2 (d, J = 6.0 Hz), 117.0 (d, J = 5.0 Hz), 60.7, 45.4, 18.3, 14.2. 31P NMR (162 MHz, CDCl3)
δ -14.7. 19F NMR (377 MHz) δ -113.0. HRMS (ESI) m/z: [M+H]+ calcd for C29H27FO2P 457.1727;
found 457.1725.

ethyl 2-(5'-chloro-2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (3c)

S12
The general procedure was applied to 1c (111.8 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and
the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the
residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the
title compound as colorless oil (113.5 mg, 80% yield).1H NMR (400 MHz, CDCl3) δ 7.34-7.27 (m, 7H),
7.25-7.16 (m, 7H), 7.13-7.08 (m, 1H), 7.03 (s, 1H), 6.95 (dd, J = 8.4, 3.2 Hz, 1H), 4.10-4.03 (m, 2H),
3.53 (q, J = 7.2 Hz, 1H), 1.32 (d, J = 7.2 Hz, 3H), 1.20 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3)
δ 174.3, 149.4 (d, J = 29.0 Hz), 140.6 (d, J = 6.0 Hz), 140.0, 137.2 (d, J = 12.0 Hz), 137.1 (d, J = 12.0
Hz), 135.4, 134.8, 134.75 (d, J = 16.0 Hz), 134.0, 133.8, 130.1 (d, J = 5.0 Hz), 128.9 (d, J = 4.0 Hz),
128.7 (d, J = 2.0 Hz), 128.55 (d, J = 1.0 Hz), 128.48 (d, J = 1.0 Hz), 128.1 (d, J = 3.0 Hz), 128.0, 127.5,
126.8, 60.7, 45.4, 18.3, 14.2. 31P NMR (162 MHz, CDCl3) δ -14.2. HRMS (ESI) m/z: [M+H]+ calcd for
C29H27ClO2P 473.1432; found 473.1422.

ethyl 2-(2'-(diphenylphosphino)-5'-(trifluoromethyl)-[1,1'-biphenyl]-3-yl)propanoate (3d)

The general procedure was applied to 1d (121.8 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and
the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the
residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the
title compound as colorless oil (124.8 mg, 82% yield). 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 3.2
Hz, 1H), 7.48 (d, J = 8.0 Hz, 1H), 7.30 (dd, J = 9.2, 3.2 Hz, 6H), 7.24-7.18 (m, 6H), 7.15-7.09 (m, 2H),
7.05 (s, 1H), 4.16-4.06 (m, 2H), 3.53 (q, J = 7.2 Hz, 1H), 1.33 (d, J = 7.2 Hz, 3H), 1.20 (t, J = 7.2 Hz,
3H). 13C NMR (100 MHz, CDCl3) δ 174.3, 148.2 (d, J = 28.0 Hz), 141.6 (d, J = 18.0 Hz), 140.6 (d, J =
5.0 Hz), 140.2, 136.5 (d, J = 12.0 Hz), 136.4 (d, J = 12.0 Hz), 134.2 (d, J = 5.0 Hz), 134.0, 130.8, 130.5,
129.0 (d, J = 2.0 Hz), 128.8, 128.64 (d, J = 2.0 Hz), 128.57 (d, J = 2.0 Hz), 128.53, 128.46, 128.1 (d, J
= 2.0 Hz), 127.1, 126.8, 126.66 -126.59 (m), 124.1(q, 1JC-F = 271.0 Hz), 123.9-123.8 (m), 122.7, 60.7,
45.4, 18.4, 14.2. 31P NMR (162 MHz, CDCl3) δ -12.5. 19F NMR (377 MHz) δ -62.6. HRMS (ESI) m/z:
[M+H]+ calcd for C30H27F3O2P 507.1695; found 507.1697.

S13
ethyl 2-(2'-(diphenylphosphino)-4'-methyl-[1,1'-biphenyl]-3-yl)propanoate (3e)
The general procedure was applied to 1e (105.7 mg, 0.3 mmol, 1 equiv) 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and
the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the
residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the
title compound as colorless oil (127.8 mg, 94% yield). 1H NMR (400 MHz, CDCl3) δ 7.31-7.26 (m,
6H), 7.25-7.18 (m, 8H), 7.14-7.10 (m, 1H), 7.04 (s, 1H), 6.84 (d, J = 4.0 Hz, 1H), 4.16-4.00 (m, 2H),
3.52 (q, J = 8.0 Hz, 1H), 2.24 (s, 3H), 1.31 (d, J = 8.0 Hz, 3H), 1.19 (t, J = 8.0 Hz, 3H). 13C NMR (100
MHz, CDCl3) δ 174.5, 145.3 (d, J = 29.0 Hz) , 141.9 (d, J = 6.0 Hz), 139.7, 137.8 (d, J = 12.0 Hz),
137.7 (d, J = 12.0 Hz), 136.9, 135.6 (d, J = 14.0 Hz), 134.5, 134.0 (d, J = 20.0 Hz), 130.1 (d, J = 5.0
Hz), 129.6, 129.3 (d, J = 4.0 Hz), 128.43 (d, J = 1.0 Hz), 128.38 (d, J = 1.0 Hz), 128.3, 127.8, 126.1,
60.7, 45.4, 21.3, 18.3, 14.2. 31P NMR (162 MHz, CDCl3) δ -12.9. HRMS (ESI) m/z: [M+H]+ calcd for
C30H30O2P 453.1978; found 453.1971.

ethyl 2-(2'-(diphenylphosphino)-4'-fluoro-[1,1'-biphenyl]-3-yl)propanoate (3f)

The general procedure was applied to 1f (106.9 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere. At ambient temperature, EtOAc (15 mL) was added, and the
mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the residue
was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title
compound ascolorless oil (116.6 mg, 85% yield). 1H NMR (400 MHz, CDCl3) δ 7.33-7.26 (m, 7H),
7.22-7.17 (m, 6H), 7.10-7.00 (m, 3H), 6.73-6.69 (m, 1H), 4.16-4.02 (m, 2H), 3.52 (q, J = 7.2 Hz, 1H),
1.31 (d, J = 7.2 Hz, 3H), 1.19 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 174.4, 162.0 (d, 1JC-F=

S14
248.0 Hz), 143.9 (d, J = 3.0 Hz), 143.6 (d, J = 3.0 Hz), 140.9 (d, J = 6.0 Hz), 139.9, 139.3 (d, J = 5.0
Hz), 139.1 (d, J = 5.0 Hz), 136.9 (d, J = 12.0 Hz), 136.7 (d, J = 12.0 Hz), 134.0 (d, J = 21.0 Hz) 131.7
(dd, J = 7.0, 4.0 Hz), 129.2 (d, J = 4.0 Hz), 128.9, 128.6 (d, J = 7.0 Hz), 128.4 (d, J = 3.0 Hz), 127.9,
126.4, 120.1 (d, 2JC-F = 22.0 Hz), 115.6 (d, 2JC-F= 21.0 Hz), 60.7,45.4,18.4,14.2. 31P NMR (162 MHz,
CDCl3) δ -12.3. 19F NMR (377 MHz) δ -114.6. HRMS (ESI) m/z: [M+H]+ calcd for C29H27FO2P
457.1727; found 457.1723.

ethyl 2-(4'-chloro-2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (3g)

The general procedure was applied to 1g (111.8 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere. At ambient temperature, EtOAc (15 mL) was added, and the
mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the residue
was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title
compound as colorless oil (100.8 mg, 71% yield). 1H NMR (400 MHz, CDCl3) δ 7.37-7.28 (m, 7H),
7.26-7.17 (m, 7H), 7.10-7.06 (m, 1H), 7.01 (s, 1H), 6.97-6.94 (m, 1H), 4.10-4.02 (m, 2H), 3.52 (q, J =
7.2 Hz, 1H), 1.31 (d, J = 7.2 Hz, 3H), 1.20 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 174.4,
146.1 (d, J = 27.0 Hz), 140.7 (d, J = 6.0 Hz), 140.0, 138.8 (d, J = 19.0 Hz), 136.8, 136.7, 136.5, 134.1,
133.9, 133.6, 133.2, 131.4 (d, J = 4.0 Hz), 129.0 (d, J = 4.0 Hz), 128.9, 128.7, 128.6 (d, J = 7.0 Hz),
128.2 (d, J = 4.0 Hz), 128.0, 126.5, 60.7, 45.4, 18.3, 14.2. 31P NMR (162 MHz, CDCl3) δ -12.3. HRMS
(ESI) m/z: [M+H]+ calcd for C29H27ClO2P 473.1432; found 473.1420.

ethyl 2-(2'-(diphenylphosphino)-4'-(trifluoromethyl)-[1,1'-biphenyl]-3-yl)propanoate (3h)

The general procedure was applied to 1h (121.8 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and

S15
the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the
residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the
title compound as colorless oil (132.4 mg, 87% yield). 1H NMR (400 MHz, CDCl3) δ 7.61 (dd, J = 8.0,
1.2 Hz, 1H), 7.41 (dd, J = 8.0, 4.0 Hz, 1H), 7.33-7.26 (m, 7H), 7.25-7.17 (m, 6H), 7.10 (dd, J = 6.0, 2.4
Hz, 1H), 7.05 (s, 1H), 4.18-4.02 (m, 2H), 3.53 (q, J = 7.2 Hz, 1H), 1.33 (d, J = 7.2 Hz, 3H), 1.20 (t, J =
7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 174.3, 151.2 (d, J = 27.0 Hz), 151.0, 140.7 (d, J = 5.0 Hz),
140.1, 138.2 (d, J = 19.0 Hz), 136.5 (d, J = 12.0 Hz), 136.3 (d, J = 12.0 Hz), 134.0 (d, 2JC-F = 20.0 Hz),
130.5 (d, J = 5.0 Hz), 130.2 (q, J = 4.0 Hz), 129.6 (d, 2JC-F= 32.0 Hz), 129.0, 128.9 (d, J = 4.0 Hz),
128.6 (d, J = 7.0 Hz), 128.1, 128.0 (d, J = 4.0 Hz),126.9, 125.4-125.3(m), 124.1 (q, 1JC-F = 271.0 Hz),
122.7, 60.8, 45.4, 18.4, 14.2. 31P NMR (162 MHz, CDCl3) δ -12.3. 19F NMR (377 MHz) δ -62.5.
HRMS (ESI) m/z: [M+H]+ calcd for C30H27F3O2P 507.1695; found 507.1691.

ethyl 2-(2'-(diphenylphosphino)-4-methoxy-[1,1'-biphenyl]-3-yl)propanoate (3i)

The general procedure was applied to 1i (110.5 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and
the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the
residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/10) to afford the
title compound as colorless oil (85.9 mg, 61% yield). 1H NMR (400 MHz, CDCl3) δ 7.40-7.35 (m, 1H),
7.34-7.19 (m, 12H), 7.14-7.09 (m, 1H), 7.03-7.01 (m, 1H), 6.98 (s, 1H), 6.78 (d, J = 8.0 Hz, 1H), 4.09
(q, J = 8.0 Hz, 2H), 3.84 (q, J = 8.0 Hz, 1H), 3.81 (s, 3H), 1.21 (d, J = 8.0 Hz, 3H), 1.18 (t, J = 8.0 Hz,
3H). 13C NMR (100 MHz, CDCl3) δ 175.0, 156.0, 148.0 (d, J = 29.0 Hz), 138.0 (d, J = 12.0 Hz), 137.8
(d, J = 12.0 Hz), 135.8 (d, J = 14.0 Hz), 134.2, 134.1, 134.07, 134.0 (d, J = 3.0 Hz), 133.8 (d, J = 3.0
Hz), 130.3 (d, J = 4.0 Hz), 129.8 (d, J = 2.0 Hz), 129.1 (d, J = 4.0 Hz), 128.7, 128.5, 128.42, 128.40,
128.3 (d, J = 3.0 Hz), 127.1, 109.7, 60.4, 55.4, 39.4, 16.7, 14.3. 31P NMR (162 MHz, CDCl3) δ -13.3.
HRMS (ESI) m/z: [M+H]+ calcd for C30H30O3P 469.1927; found 469.1923.

S16
ethyl 2-(2'-(diphenylphosphino)-4-phenoxy-[1,1'-biphenyl]-3-yl)propanoate (3j)
The general procedure was applied to 1i (129.2 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere. At ambient temperature, EtOAc (15 mL) was added, and the
mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the residue
was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/15) to afford the title
compound as colorless oil (100.4 mg, 63% yield). 1H NMR (400 MHz, CDCl3) δ 7.41-7.36 (m, 1H),
7.35-7.19 (m, 14H), 7.15 (s, 1H), 7.11-7.04 (m, 2H), 7.00 (dd, J = 7.6, 4.0 Hz, 1H), 6.92 (d, J = 7.6 Hz,
2H), 6.76 (d, J = 8.4 Hz, 1H), 4.09-3.95 (m, 2H), 3.91 (q, J = 7.2 Hz, 1H), 1.26 (d, J = 4.0 Hz 3H), 1.13
(t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 174.5, 157.6, 153.3, 147.2 (d, J = 27.0 Hz), 137.6,
137.4 (d, J = 2.0 Hz), 137.3, 137.28(d, J = 2.0 Hz),136.1 (d, J = 14.0 Hz), 134.1 (d, J = 20.0 Hz), 133.8,
131.5, 130.3 (d, J = 5.0 Hz), 130.2 (d, J = 5.0 Hz), 129.6, 128.4 (d, J = 3.0 Hz), 128.7, 128.6 (d, J = 4.0
Hz), 128.4 (d, J = 3.0 Hz), 128.36 (d, J = 3.0 Hz), 127.4, 122.9, 118.4, 118.2, 60.6, 39.3, 17.1, 14.2. 31P
NMR (162 MHz, CDCl3) δ -12.0. HRMS (ESI) m/z: [M+H]+ calcd for C35H32O3P 531.2084; found
531.2078.

ethyl 2-(2'-(diphenylphosphino)-4-(methylthio)-[1,1'-biphenyl]-3-yl)propanoate (3k)

The general procedure was applied to 1j (115.4 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere. At ambient temperature, EtOAc (15 mL) was added, and the
mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the residue
was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title
compound as colorless oil (129.5 mg, 89% yield). 1H NMR (400 MHz, CDCl3) δ 7.23-7.21 (m, 6H),
7.17-7.11 (m, 8H), 7.06-7.04 (m, 1H), 6.95 (s, 1H), 6.76 (d, J = 4.8 Hz, 1H), 4.07-3.94 (m, 2H), 3.44 (q,
J = 7.2 Hz, 1H), 2.17 (s, 3H), 1.23 (d, J = 8.0 Hz, 3H), 1.11 (t, J = 8.0 Hz, 3H). 13C NMR (100 MHz,
CDCl3) δ 174.6, 145.3 (d, J = 28.0 Hz), 142.0 (d, J = 6.0 Hz), 139.8, 137.9 (d, J = 12.0 Hz), 137.7 (d, J
= 11.0 Hz), 137.1, 135.6 (d, J = 15.0 Hz), 134.6, 130.1 (d, J = 5.0 Hz), 129.7, 129.3 (d, J = 4.0 Hz),
128.54-128.47(m), 128.4 (d, J = 1.0 Hz), 127.9, 126.2, 60.8, 45.5, 21.4, 18.4, 14.3. 31P NMR (162 MHz,
CDCl3) δ -13.1. HRMS (ESI) m/z: [M+H]+ calcd for C30H30O2PS 485.1699; found 485.1693.

S17
ethyl 2-(4-bromo-2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (3l)
The general procedure was applied to 1k (125.2 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere. At ambient temperature, EtOAc (15 mL) was added, and the
mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the residue
was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title
compound as colorless oil (124.1 mg, 80% yield). 1H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 8.4 Hz,
1H), 7.41-7.35 (m, 1H), 7.34-7.25 (m, 8H), 7.19 (m, 4H), 7.12 (d, J = 0.8 Hz, 1H), 7.04-7.01 (m, 1H),
7.00-6.96 (m, 1H), 4.13-4.05 (m, 3H), 1.24 (d, J = 8.0 Hz, 3H), 1.19 (t, J = 8.0 Hz, 3H). 13C NMR (100
MHz, CDCl3) δ 173.8, 146.8 (d, J = 28.0 Hz), 141.3 (d, J = 6.0 Hz), 139.2, 137.4 (d, J = 12.0 Hz), 137.2
(d, J = 11.0 Hz), 135.8 (d, J = 14.0 Hz), 134.2, 134.0 (d, J = 4.0 Hz), 133.8 (d, J = 3.0 Hz), 132.2, 130.1,
130.0, 129.95, 129.7 (d, J = 4.0 Hz), 128.8, 128.6 (d, J = 3.0 Hz), 128.5 (d, J = 2.0 Hz),128.4 (d, J = 2.0
Hz), 127.8, 123.5, 60.9, 44.7, 17.3, 14.2. 31P NMR (162 MHz, CDCl3) δ -13.2. HRMS (ESI) m/z:
[M+H]+ calcd for C29H27BrO2P 517.0927; found 517.0925.

methyl 2'-(diphenylphosphino)-3-(1-ethoxy-1-oxopropan-2-yl)-[1,1'-biphenyl]-4-carboxylate (3m)

The general procedure was applied to 1l (118.9 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and
the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the
residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/15) to afford the
title compound as colorless oil (107.4 mg, 72% yield). 1H NMR (400 MHz, CDCl3) δ 7.85 (d, J = 8.0
Hz, 1H), 7.42-7.38 (m, 1H), 7.31-7.28 (m, 8H), 7.21-7.18 (m, 6H), 7.06-7.03 (m, 1H), 4.50 (q, J = 8.0
Hz, 1H), 4.07-4.03 (m, 2H), 3.87 (s, 3H), 1.28 (d, J = 8.0 Hz, 3H), 1.17 (t, J = 8.0 Hz, 3H). 13C NMR
(100 MHz, CDCl3) δ 174.4, 167.8, 147.0 (d, J = 28.0 Hz), 145.7 (d, J = 5.0 Hz), 141.4, 137.4 (d, J =
12.0 Hz), 137.2 (d, J = 12.0 Hz), 135.8 (d, J = 15.0 Hz), 134.2, 134.0 (d, J = 4.0 Hz), 133.8 (d, J = 4.0

S18
Hz), 130.3, 130.2 (d, J = 5.0 Hz), 129.9 (d, J = 4.0 Hz), 128.8, 128.6 (d, J = 2.0 Hz),128.5 (d, J = 1.0
Hz), 128.4 (d, J = 1.0 Hz), 128.0 (d, J = 4.0 Hz), 127.9, 127.7, 60.6, 52.0, 42.1, 17.6, 14.2. 31P NMR
(162 MHz, CDCl3) δ -13.3. HRMS (ESI) m/z: [M+H]+ calcd for C31H30O4P 497.1876; found 497.1864.

ethyl 2-(2'-(diphenylphosphino)-4-(trifluoromethyl)-[1,1'-biphenyl]-3-yl)propanoate (3n)

The general procedure was applied to 1m (121.8 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and
the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the
residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the
title compound as colorless oil (136.9 mg, 90% yield). 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 8.0
Hz, 1H), 7.42-7.38 (m, 1H), 7.36 (s, 1H), 7.33-7.26 (m, 9H), 7.21-7.17 (m, 4H), 7.04 (dd, J = 7.6, 4.4
Hz, 1H), 4.18-4.02 (m, 3H), 1.26 (d, J = 2.4 Hz, 3H), 1.16 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz,
CDCl3) δ 173.8, 146.4 (d, J = 27.0 Hz), 145.5 (d, J = 6.0 Hz), 138.9, 137.1 (d, J = 12.0 Hz), 136.8 (d, J
= 12.0 Hz), 135.8 (d, J = 16.0 Hz), 134.1, 134.0 (d, J = 1.0 Hz), 133.9, 133.8 (d, J = 1.0 Hz), 130.3 (d, J
= 4.0 Hz), 130.0 (d, J = 5.0 Hz), 129.4 (d, J = 4.0 Hz), 128.9 (d, J = 2.0 Hz), 128.8, 128.7 (d, J = 6.0
Hz), 128.5 (d, J = 7.0 Hz), 128.2 (d, J = 4.0 Hz), 128.0, 127.8 (d, J = 4.0 Hz), 127.0, 126.7,
125.4-125.2(m), 124.4 (q, 1JC-F = 272.0 Hz), 60.9, 40.9, 18.9, 14.1. 31P NMR (162 MHz, CDCl3) δ -13.0.
19F NMR (377 MHz, CDCl3) δ -58.7. HRMS (ESI) m/z: [M+H]+ calcd for C30H27F3O2P 507.1695;
found 507.1686.

ethyl 2-(3-(2-(diphenylphosphino)phenyl)naphthalen-1-yl)propanoate (3o)

The general procedure was applied to 1n (116.5 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere. At ambient temperature, EtOAc (15 mL) was added, and the
mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the residue

S19
was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title
compound as colorless oil (91.0 mg, 62% yield). 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.4 Hz,
1H), 7.66 (d, J = 8.0 Hz, 1H), 7.55 (s, 1H), 7.52-7.46 (m, 1H), 7.45-7.40 (m, 3H), 7.35 (s, 1H),
7.31-7.20 (m, 11H), 7.10 (dd, J = 7.6, 3.6 Hz, 1H), 4.37 (q, J = 7.2 Hz, 1H), 4.14-4.04 (m, 2H), 1.44 (d,
J = 8.0 Hz, 3H), 1.14 (t, J = 8.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 174.9, 148.1 (d, J = 29.0 Hz),
138.9 (d, J = 7.0 Hz), 137.9 (d, J = 12.0 Hz), 137.7 (d, J = 12.0 Hz), 136.1, 136.0, 135.9, 134.4, 134.1
(d, J = 5.0 Hz), 133.9 (d, J = 5.0 Hz), 133.4, 130.5, 130.4 (d, J = 5.0 Hz) 129.2, 128.8, 128.5, 128.5 (d, J
= 2.0 Hz), 128.4 (d, J = 2.0 Hz), 128.35, 127.5, 126.9 (d, J = 4.0 Hz), 126.3, 125.8, 123.1, 60.8, 41.5,
17.6, 14.2. 31P NMR (162 MHz, CDCl3) δ -13.4. HRMS (ESI) m/z: [M+H]+ calcd for C33H30O2P
489.1978; found 489.1971.

ethyl 2-(2'-(dicyclohexylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (3p)

The general procedure was applied to 1p (105.0 mg, 0.3 mmol, 1 equiv), 2a (54.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere. At ambient temperature, EtOAc (15 mL) was added, and the
mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the residue
was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title
compound as a white solid (78.5 mg, 58% yield). 1H NMR (400 MHz, CDCl3) δ 7.59-7.57 (m, 1H),
7.36-7.30 (m, 3H), 7.26-7.24 (m, 2H), 7.19 (s, 1H), 4.17-4.06 (m, 2H), 3.73 (q, J = 8.0 Hz, 1H),
1.82-1.80 (m, 2H), 1.68-1.61 (m, 10H), 1.51 (d, J = 8.0 Hz, 3H), 1.25-1.02 (m, 13H). 13C NMR (100
MHz, CDCl3) δ 174.6, 150.4 (d, J = 28.0 Hz), 143.1 (d, J = 6.0 Hz), 139.6, 134.0 (d, J = 22.0 Hz), 132.9,
130.2 (d, J = 5.0 Hz), 129.6-129.5 (m), 129.1, 128.4, 128.2, 127.3, 126.5, 125.9, 60.7, 45.5, 34.6-34.4
(m), 30.5-30.2 (m), 29.2 (d, J = 9.0 Hz), 27.3-27.1 (m), 26.4, 18.6, 14.2. 31P NMR (162 MHz, CDCl3) δ
-13.0. HRMS (ESI) m/z: [M+H]+ calcd for C29H40O2P 451.2760; found 451.2752.

butyl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (4a)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2b (188.1 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09

S20
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and
the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the
residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the
title compound as colorless oil (127.5 mg, 91% yield). 1H NMR (400 MHz, CDCl3) δ 7.40-7.36 (m,
1H), 7.32-7.25 (m, 8H), 7.24-7.19 (m, 6H), 7.15-7.11 (m, 1H), 7.04 (m, 2H), 4.03 (td, J = 6.0, 4.0 Hz,
2H), 3.53 (q, J = 8.0 Hz, 1H), 1.59-1.50 (m, 2H), 1.32 (d, J = 8.0 Hz, 3H), 1.30-1.27 (m, 2H), 0.87 (t, J
= 8.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 174.5, 148.0 (d, J = 29.0 Hz), 141.9 (d, J = 6.0 Hz),
139.8, 137.8 (d, J = 12.0 Hz), 137.6 (d, J = 12.0 Hz), 135.9 (d, J = 15.0 Hz), 134.1 (d, J = 1.0 Hz),
133.9 (d, J = 2.0 Hz), 130.1 (d, J = 4.0 Hz), 129.2 (d, J = 4.0 Hz), 128.7, 128.5 (d, J = 2.0 Hz), 128.4 (d,
J = 1.0 Hz), 128.34 (d, J = 1.0 Hz), 128.3 (d, J = 2.0 Hz), 127.8, 127.4, 126.3, 64.6, 45.4, 30.6, 19.1,
18.2, 13.7. 31P NMR (162 MHz, CDCl3) δ -13.1. HRMS (ESI) m/z: [M+H]+ calcd for C31H32O2P
467.2134; found 467.2130.

3-phenylpropyl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (4b)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2c (243.9 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol), KOAc (58.8 mg, 0.6 mmol, 2.0 equiv) in toluene (2.0 mL) was stirred at 140℃ in heating
mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was added, and
the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo and the
residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the
title compound as colorless oil (127.0 mg, 80% yield). 1H NMR (400 MHz, CDCl3) δ 7.38-7.34 (m,
1H), 7.31-7.24 (m, 8H), 7.24-7.18 (m, 8H), 7.16-7.13 (m, 2H), 7.08 (s, 1H), 7.04 (d, J = 4.0 Hz, 3H),
4.03 (t, J = 8.0 Hz, 2H), 3.55 (q, J = 8.0 Hz, 1H), 2.59-2.51 (m, 2H), 1.87 (m, 2H), 1.33 (d, J = 8.0 Hz,
3H). 13C NMR (100 MHz, CDCl3) δ 174.4, 148.0 (d, J = 28.0 Hz), 142.0 (d, J = 6.0 Hz), 141.2, 139.8,
137.8 (d, J = 12.0 Hz), 137.6 (d, J = 12.0 Hz), 135.9 (d, J = 14.0 Hz), 134.1 (d, J = 3.0 Hz), 133.9 (d, J
= 3.0 Hz), 130.2 (d, J = 4.0 Hz), 129.2 (d, J = 5.0 Hz), 128.7, 128.5 (d, J = 1.0 Hz), 128.46, 128.42,
128.4 (d, J = 2.0 Hz), 127.9, 127.5, 126.4, 126.0, 63.9, 45.5, 32.0, 30.2, 18.1. 31P NMR (162 MHz,
CDCl3) δ -13.1. HRMS (ESI) m/z: [M+H]+ calcd for C36H34O2P 529.2291; found 529.2282.

S21
benzyl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (4c)
The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2d (218.7 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title compound as colorless oil (108.3 mg,
72% yield). 1H NMR (400 MHz, CDCl3) δ 7.40-7.35 (m, 2H), 7.29-7.25 (m, 9H), 7.21 (m, 9H),
7.16-7.13 (m, 1H), 7.06-7.02 (m, 2H), 5.07 (m, 2H), 3.60 (q, J = 8.0 Hz, 1H), 1.34 (d, J = 8.0 Hz, 3H).
13C NMR (100 MHz, CDCl3) δ 174.2, 148.0 (d, J = 28.0 Hz), 142.0 (d, J = 7.0 Hz), 139.5, 137.7 (d, J =
12.0 Hz), 137.6 (d, J = 12.0 Hz), 136.1, 135.9 (d, J = 14.0 Hz), 134.1 (d, J = 3.0 Hz), 133.9 (d, J = 2.0
Hz), 130.2 (d, J = 4.0 Hz), 129.2 (d, J = 4.0 Hz), 128.7, 128.5, 128.4 (d, J = 6.0 Hz), 127.4, 126.4, 66.4,
45.4, 18.2. 31P NMR (162 MHz, CDCl3) δ -13.1. HRMS (ESI) m/z: [M+H]+ calcd for C34H30O2P
501.1978; found 501.1966.

cyclopentyl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (4d)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2e (198.9 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title compound as colorless oil (125.1 mg,
87% yield). 1H NMR (400 MHz, CDCl3) δ 7.39-7.35 (m, 1H), 7.29 (s, 8H), 7.23-7.19 (m, 6H), 7.11 (d,
J = 4.0 Hz, 1H), 7.04 (t, J = 4.0 Hz, 2H), 5.12 (t, J = 8.0 Hz, 1H), 3.49 (q, J = 8.0 Hz, 1H), 1.80-1.52 (m,
8H), 1.30 (d, J = 8.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 174.2, 148.1 (d, J = 28.0 Hz), 141.9 (d, J
= 7.0 Hz), 139.9, 137.8 (d, J = 12.0 Hz), 137.7 (d, J = 12.0 Hz), 137.8 (d, J = 12.0 Hz), 135.9 (d, J =
15.0 Hz), 134.1, 133.9, 130.1 (d, J = 4.0 Hz), 129.2 (d, J = 4.0 Hz), 128.7, 128.53, 128.5, 128.5 (d, J =

S22
2.0 Hz), 128.4 (d, J = 2.0 Hz), 128.3 (d, J = 3.0 Hz),127.8, 127.4, 126.3, 45.6, 32.6, 23.74, 23.68, 18.1.
31P NMR (162 MHz, CDCl3) δ -13.3. HRMS (ESI) m/z: [M+H]+ calcd for C32H32O2P 479.2134; found
479.2130.

cyclohexyl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (4e)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2f (211.5 mg 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title compound as colorless oil (122.8 mg,
83% yield). 1H NMR (400 MHz, CDCl3) δ 7.39-7.36 (m, 1H), 7.29 (m, 8H), 7.24-7.18 (m, 6H), 7.12 (d,
J = 3.6 Hz, 1H), 7.05-7.03 (m, 2H), 4.76-4.71 (m, 1H), 3.55-3.50 (m, 1H), 1.77 (m, 1H), 1.73-1.38 (m,
6H), 1.35-1.23 (m, 6H). 13C NMR (100 MHz, CDCl3) δ 173.9, 148.1 (d, J = 28.0 Hz), 141.9 (d, J = 7.0
Hz), 140.0, 137.8 (d, J = 13.0 Hz), 137.7 (d, J = 12.0 Hz), 136.0 (d, J = 15.0 Hz), 134.0 (d, J = 20.0 Hz),
130.1 (d, J = 5.0 Hz), 129.2 (d, J = 4.0 Hz), 128.7, 128.5 (d, J = 3.0 Hz), 128.4 (d, J = 7.0 Hz), 128.2 (d,
J = 4.0 Hz), 127.8, 127.4, 126.3, 72.6, 45.7, 31.4, 25.4, 23.5, 18.2. 31P NMR (162 MHz, CDCl3) δ -13.3.
HRMS (ESI) m/z: [M+H]+ calcd for C33H34O2P 493.2291; found 493.2284.

(3s,5s,7s)-adamantan-1-yl 2-(2'-(diphenylphosphanyl)-[1,1'-biphenyl]-3-yl)propanoate (4f)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2g (258.3 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title compound as a white solid (112.7 mg,
69% yield). 1H NMR (400 MHz, CDCl3) δ 7.41-7.37 (m, 1H), 7.33-7.26 (m, 8H), 7.24-7.19 (m, 8H),
7.11-7.03 (m, 3H), 3.46-3.41 (m, 1H), 2.10-2.03 (m, 9H), 1.66 (s, 1H), 1.61 (s, 5H), 1.26 (d, 7.2 Hz,
3H). 13C NMR (100 MHz, CDCl3) δ 173.7, 148.3 (d, J = 28.6 Hz), 141.9 (d, J = 5.9 Hz), 140.5, 138.0,
137.8 (d, J = 4.2 Hz), 137.7, 136.0 (d, J = 14.3 Hz), 134.2, 134.2, 134.0 (d, J = 2.0 Hz), 130.2 (d, J =

S23
4.8 Hz), 129.3 (d, J = 3.7 Hz), 128.8, 128.6, 128.6, 128.5, 128.5, 128.4 (d, J = 2.2 Hz), 128.2 (d, J = 3.8
Hz), 127.8, 127.5, 126.3, 80.6, 46.5, 41.3, 36.3, 30.9, 18.4. 31P NMR (162 MHz, CDCl3) δ -13.4.
HRMS (ESI) m/z: [M+H]+ calcd for C37H38O3P 545.2604; found 545.2600.

tert-butyl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (4g)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2h (188.1 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg,
0.09 mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title compound as colorless oil (123.3 mg,
88% yield). 1H NMR (400 MHz, CDCl3) δ 7.39-7.35 (m, 1H), 7.29 (m, 7H), 7.25-7.18 (m, 7H),
7.12-7.09 (m, 1H), 7.06-7.01 (m, 2H), 3.44 (q, J = 8.0 Hz, 1H), 1.38 (s, 9H), 1.27 (d, J = 8.0 Hz, 3H).
13C NMR (100 MHz, CDCl3) δ 173.8, 148.2 (d, J = 29.0 Hz), 141.8 (d, J = 6.0 Hz), 140.3, 137.8 (d, J =
13.0 Hz), 137.7 (d, J = 12.0 Hz), 136.0 (d, J = 15.0 Hz), 134.0 (d, J = 20.0 Hz), 130.1 (d, J = 5.0 Hz),
129.2 (d, J = 4.0 Hz), 128.7, 128.5 (d, J = 1.0 Hz), 128.43 (d, J = 1.0 Hz), 128.37 (d, J = 1.0 Hz), 128.2
(d, J = 4.0 Hz), 127.7, 127.4, 126.2, 80.4, 46.4, 28.0, 18.3. 31P NMR (162 MHz, CDCl3) δ -13.2.
HRMS (ESI) m/z: [M+H]+ calcd for C31H32O2P 467.2134; found 467.2133.

phenyl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (4h)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2i (206.1 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title compound as a white solid (54.1 mg,
37% yield). 1H NMR (400 MHz, CDCl3) δ 7.41-7.37 (m, 1H), 7.33-7.27 (m, 12H), 7.23-7.17 (m, 7H),
7.06-7.03 (m, 1H), 7.01-6.98 (m, 2H), 3.78 (q, J = 8.0 Hz, 1H), 1.44 (d, J = 8.0 Hz, 3H). 13C NMR (100
MHz, CDCl3) δ 172.9, 150.87, 147.8 (d, J = 28.0 Hz), 142.2 (d, J = 6.0 Hz), 139.2, 137.6 (d, J = 12.0
Hz), 137.5 (d, J = 12.0 Hz), 136.0 (d, J = 15.0 Hz), 134.1 (d, J = 2.0 Hz),134.0, 133.9 (d, J = 2.0 Hz),
130.1 (d, J = 5.0 Hz), 129.3, 129.2 (d, J = 4.0 Hz), 128.7, 128.6 (d, J = 4.0 Hz),128.5 (d, J = 2.0 Hz),

S24
128.4 (d, J = 7.0 Hz), 128.1, 127.5, 126.3, 125.7, 121.5, 45.5, 18.2. 31P NMR (162 MHz, CDCl3) δ
-13.1. HRMS (ESI) m/z: [M+H]+ calcd for C33H28O2P 487.1821; found 487.1814.

ethyl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)butanoate (4i)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2j (175.5 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title compound as colorless oil (122.4 mg,
90% yield). 1H NMR (400 MHz, CDCl3) δ 7.40-7.36 (m, 1H), 7.34-7.25 (m, 8H), 7.22-7.18 (m, 6H),
7.17-7.13 (m, 1H), 7.07 (s, 1H), 7.04-7.01 (m, 1H), 4.17-4.01 (m, 2H), 3.25 (t, J = 7.6 Hz, 1H),
1.98-1.83 (m, 1H), 1.64-1.53 (m, 1H), 1.19 (t, J = 8.0 Hz, 3H), 0.79 (t, J = 8.0 Hz, 3H). 13C NMR (100
MHz, CDCl3) δ 174.0, 148.0 (d, J = 28.0 Hz),141.9 (d, J = 6.0 Hz), 138.4, 137.7 (d, J = 13.0 Hz), 137.6
(d, J = 12.0 Hz), 135.8 (d, J = 15.0 Hz), 134.1, 133.9, 130.2 (d, J = 5.0 Hz), 129.6 (d, J = 4.0 Hz), 128.7,
128.5 (d, J = 3.0 Hz), 128.4, 128.3, 127.8, 127.4, 126.7, 60.6, 53.4, 26.7, 14.2, 12.2. 31P NMR (162
MHz, CDCl3) δ -13.1. HRMS (ESI) m/z: [M+H]+ calcd for C30H30O2P 453.1978; found 453.1970.

ethyl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)pentanoate (4j)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2k (188.1 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL was stirred at 140℃ in heating mantle for 24 h under an atmosphere of argon.
At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short pad of
silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title compound as colorless oil (121.9 mg,
87% yield). 1H NMR (400 MHz, CDCl3) δ 7.40-7.36 (m, 1H), 7.33-7.26 (m, 8H), 7.24-7.16 (m, 7H),
7.08 (s, 1H), 7.04-7.01 (m, 1H), 4.16-4.01 (m, 2H), 3.36 (t, J = .0 Hz, 1H), 1.92-1.81 (m, 1H), 1.62-1.50
(m, 1H), 1.21-1.15 (m, 5H), 0.86 (t, J = 8.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 174.1, 148.0 (d, J
= 28.0 Hz), 141.9 (d, J = 6.0 Hz), 138.6, 137.7 (d, J = 12.0 Hz), 137.6 (d, J = 12.0 Hz), 135.8 (d, J =
15.0 Hz), 134.1, 134.0 (d, J = 3.0 Hz), 133.8 (d, J = 2.0 Hz), 130.2 (d, J = 5.0 Hz), 129.6 (d, J = 4.0 Hz),

S25
128.7, 128.5 (d, J = 4.0 Hz), 128.4 (d, J = 3.0 Hz), 128.3 (d, J = 2.0 Hz), 127.8, 127.4, 126.6, 60.6, 51.5,
35.6, 20.8, 14.2, 13.9. 31P NMR (162 MHz, CDCl3) δ -13.1. HRMS (ESI) m/z: [M+H]+ calcd for
C31H32O2P 467.2134; found 467.2125.

ethyl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)octanoate (4k)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2l (225.9 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title compound as colorless oil (123.8 mg,
81% yield). 1H NMR (400 MHz, CDCl3) δ 7.40-7.36 (m, 1H), 7.33-7.27 (m, 8H), 7.21 (m, 6H),
7.16-7.12 (m, 1H), 7.09 (s, 1H), 7.05-7.02 (m, 1H), 4.16-4.01 (m, 2H), 3.34 (dd, J = 8.4, 7.2 Hz, 1H),
1.96-1.84 (m, 1H), 1.61-1.52 (m, 1H), 1.31-1.15 (m, 11H), 0.86 (t, J = 8.0 Hz, 3H). 13C NMR (100
MHz, CDCl3) δ 174.1, 148.1 (d, J = 28.0 Hz), 141.9 (d, J = 6.0 Hz), 138.7, 137.8 (d, J = 13.0 Hz), 137.7
(d, J = 12.0 Hz), 137.71, 135.9 (d, J = 15.0 Hz), 134.1, 133.9 (d, J = 20.0 Hz), 130.2 (d, J = 4.0 Hz),
129.6 (d, J = 4.0 Hz), 128.7, 128.5 (d, J = 3.0 Hz), 128.4 (d, J = 1.0 Hz), 128.35, 127.8, 127.4, 126.6,
60.6, 51.7, 33.5, 31.7, 29.1, 27.6, 22.6, 14.2 ,14.1. 31P NMR (162 MHz, CDCl3) δ -13.2. HRMS (ESI)
m/z: [M+H]+ calcd for C34H38O2P 509.2604; found 509.2601.

ethyl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)-3-phenylpropanoate (4l)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2m (231.3 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title compound as colorless oil (134.5 mg,
87% yield). 1H NMR (400 MHz, CDCl3) δ 7.40-7.36 (m, 1H), 7.31-7.28 (m, 7H), 7.24-7.16 (m, 11H),
7.13 (s, 1H), 7.08-7.02 (m, 3H), 4.09-3.93 (m, 2H), 3.67 (dd, J = 9.6, 6.0 Hz, 1H), 3.16 (dd, J = 13.6,
9.6 Hz, 1H), 2.80 (dd, J = 13.6, 6.0 Hz, 1H), 1.08 (t, J = 8.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ

S26
173.2, 148.0 (d, J = 28.0 Hz), 142.1 (d, J = 6.0 Hz), 139.3, 138.1, 137.8 (d, J = 13.0 Hz), 137.6 (d, J =
12.0 Hz), 135.8 (d, J = 14.0 Hz), 134.2, 134.1 (d, J = 2.0 Hz), 133.9 (d, J = 2.0 Hz), 130.2 (d, J = 5.0
Hz), 129.5 (d, J = 4.0 Hz), 129.1, 128.7, 128.6, 128.5 (d, J = 2.0 Hz), 128.47, 128.4 (d, J = 2.0 Hz),
128.3, 127.9, 127.5, 126.8, 126.3, 60.7, 53.6, 39.8, 14.1. 31P NMR (162 MHz, CDCl3) δ -13.2. HRMS
(ESI) m/z: [M+H]+ calcd for C35H32O2P 515.2134; found 515.2125.

N-butyl-2-(2'-(diphenylphosphoryl)-[1,1'-biphenyl]-3-yl)propanamide (4m)
The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2n (187.2 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.3, EA/hexane = 1/3), then oxidized by hydrogen peroxide to afford the title
compound as a white solid (109.9 mg, 76% yield). 1H NMR (400 MHz, CDCl3) δ 7.58 (t, J = 7.6 Hz,
1H), 7.54-7.41 (m, 7H), 7.39-7.32 (m, 6H), 7.07 (d, J = 7.8 Hz, 1H), 6.92 (t, J = 7.6 Hz, 1H), 6.79 (s,
1H), 6.74 (d, J = 7.6 Hz, 1H), 3.52 (q, J = 8.0 Hz, 1H), 3.33-3.15 (m, 2H), 1.52 (dt, J = 15.2, 7.6 Hz,
2H), 1.44 (d, J = 8.0 Hz, 3H), 1.35-1.29 (m, 2H), 0.88 (t, J = 8.0 Hz, 3H). 13C NMR (100 MHz, CDCl3)
δ 174.4, 147.8 (d, J = 8.0 Hz), 140.0 (d, J = 4.0 Hz), 139.8, 133.9 (d, J = 13.0 Hz), 131.9 (d, J = 2.0 Hz),
131.64, 131.6 (d, J = 2.0 Hz), 131.54, 131.48, 131.1, 128.3 (d, J = 4.0 Hz), 128.2 (d, J = 4.0 Hz), 127.8
(d, J = 6.0 Hz), 126.7, 126.6, 47.1, 39.7, 31.7, 20.2, 18.0, 13.9. 31P NMR (162 MHz, CDCl3) δ 29.1.
HRMS (ESI) m/z: [M+H]+ calcd for C31H33NO2P 482.2243; found 482.2236.

methyl 2-(2-(2'-(diphenylphosphoryl)-[1,1'-biphenyl]-3-yl)propanamido)-3-phenylpropanoate (4n)

The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2o (282.6 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.2, EA/hexane = 1/3), then oxidized by hydrogen peroxide to afford the title
compound as a white solid (75.9 mg, 43% yield). 1H NMR (400 MHz, CDCl3) δ 7.59-7.49 (m, 5H),

S27
7.44-7.39 (m, 2H), 7.35-7.32 (m, 7H), 7.23-7.15 (m, 3H), 7.09-7.07 (m, 2H), 7.04-6.94 (m, 2H),
6.92-6.86 (m, 1H), 6.79 (d, J = 7.6 Hz, 1H), 4.78 (dd, J = 14.0, 6.8 Hz, 1H), 3.64 (s, 3H), 3.44 (q, J =
7.2 Hz, 1H), 3.13 (d, J = 6.6 Hz, 2H), 1.37 (d, J = 4.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 174.1,
172.2, 147.6 (d, J = 9.0 Hz), 140.2 (d, J = 4.0 Hz), 139.1, 136.8, 133.9 (d, J = 12.0 Hz), 133.4, 132.3,
131.8, 131.7, 131.6 (d, J = 4.0 Hz), 131.3, 130.8, 129.2, 128.4, 128.3, 128.27, 128.2, 127.7, 126.7,
126.6, 126.5, 53.8, 52.1, 46.6, 37.1, 18.0. 31P NMR (162 MHz, CDCl3) δ 28.6. HRMS (ESI) m/z:
[M+H]+ calcd for C37H35NO4P 588.2298; found 588.2296.

2-(2'-(diphenylphosphoryl)-[1,1'-biphenyl]-3-yl)-N,N-dimethylpropanamide (4o)
The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2p (162.0 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.3, EA/hexane = 1/3), then oxidized by hydrogen peroxide to afford the title
compound as a white solid (87.2 mg, 64% yield). 1H NMR (400 MHz, CDCl3) δ 7.59-7.51 (m, 5H),
7.41-7.30 (m, 10H), 7.14-7.09 (m, 1H), 7.01-6.95 (m, 2H), 3.80 (q, J = 8.0 Hz, 1H), 2.94 (s, 3H), 2.86
(s, 3H), 1.32 (d, J = 4.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 173.7, 147.5 (d, J = 9.0 Hz), 140.8 (d,
J = 4.0 Hz), 140.5, 134.3 (d, J = 12.0 Hz), 133.5 (d, J = 4.0 Hz), 133.4 (d, J = 4.0 Hz), 132.3, 132.2,
131.9, 131.8 (d, J = 2.0 Hz), 131.7, 131.6, 131.55, 131.46, 131.28, 131.25, 131.22, 130.9, 129.8, 128.6,
128.2 (d, J = 1.0 Hz), 128.1, 127.9, 126.7, 126.6, 125.7, 42.9, 37.4, 35.9, 20.5. 31P NMR (162 MHz,
CDCl3) δ 28.8. HRMS (ESI) m/z: [M+H]+ calcd for C29H29NO2P 454.1930; found 454.1929.

2-(2'-(diphenylphosphoryl)-[1,1'-biphenyl]-3-yl)-N-methyl-N-phenylpropanamide (4p)
The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2q (217.8 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.3, EA/hexane = 1/3), then oxidized by hydrogen peroxide to afford the title
compound as a white solid (74.3 mg, 48% yield). 1H NMR (400 MHz, CDCl3) δ 7.50-7.41 (m, 5H),

S28
7.25-7.15 (m, 14H), 6.86-6.83 (m, 2H), 6.78 (s, 1H), 6.66(d, J = 4.0 Hz, 1H), 3.39 (q, J = 6.8 Hz, 1H),
3.15 (s, 3H), 1.16 (d, J = 4.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 174.0, 147.7 (d, J = 9.0 Hz),
143.8, 140.7, 134.3 (d, J = 12.0 Hz), 133.6, 132.5, 132.2 (d, J = 9.0 Hz), 131.8, 131.73, 131.7 (d, J = 2.0
Hz),131.6, 131.3, 129.6, 129.1, 128.2 (d, J = 11.0 Hz), 127.9, 127.4, 126.7, 126.6 (d, J = 5.0 Hz), 42.9,
37.8, 20.2. 31P NMR (162 MHz, CDCl3) δ 28.2. HRMS (ESI) m/z: [M+H]+ calcd for C34H31NO2P
516.2087; found 516.2072.

2-(2'-(diphenylphosphoryl)-[1,1'-biphenyl]-3-yl)-1-morpholinopropan-1-one (4q)
The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2r (199.8 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/10), then oxidized by hydrogen peroxide to afford the title
compound as a white solid (115.9 mg, 78% yield). 1H NMR (400 MHz, CDCl3) δ 7.53-7.42 (m, 5H),
7.38-7.34 (m, 1H), 7.29-7.22 (m, 9H), 7.01 (d, J = 4.0 Hz, 1H), 6.94-6.88 (m, 2H), 3.70(q, J = 8.0 Hz,
1H) , 3.64-3.52 (m, 2H), 3.50-3.41 (m, 3H), 3.34-3.29 (m, 1H), 3.17-3.13 (m, 2H), 1.27 (d, J = 8.0 Hz,
3H). 13C NMR (100 MHz, CDCl3) δ 172.4, 147.5 (d, J = 9.0 Hz), 141.0 (d, J = 5.0 Hz), 140.4, 134.4 (d,
J = 13.0 Hz), 133.5(d, J = 11.0 Hz), 132.4 (d, J = 10.0 Hz), 132.2 (d, J = 10.0 Hz), 132.0 (d, J = 2.0 Hz),
131.8 (d, J = 10.0 Hz),131.6, 131.5, 131.4 (d, J = 2.0 Hz), 131.0, 130.0, 128.7, 128.4, 128.3 (d, J = 4.0
Hz), 128.1 (d, J = 7.0 Hz), 126.8 (d, J = 12.0 Hz), 125.6, 66.7 (d, J = 33.0 Hz), 46.1, 43.0, 42.4, 20.5.
31P NMR (162 MHz, CDCl3) δ 28.9. HRMS (ESI) m/z: [M+H]+ calcd for C31H31NO3P 496.2036;
found 496.2029.

2-(2'-(diphenylphosphoryl)-[1,1'-biphenyl]-3-yl)-1-(indolin-1-yl)propan-1-one (4r)
The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2s (228.6 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.3, EA/hexane = 1/5), then oxidized by hydrogen peroxide to afford the title
compound as a white solid (123.6 mg, 78% yield). 1H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 8.0 Hz,

S29
1H), 7.59-7.48 (m, 5H), 7.43 (s, 1H), 7.40-7.30 (m, 7H), 7.21 (d, J = 7.2 Hz, 3H), 7.16-7.12 (m, 2H),
7.08 (dd, J = 6.5, 1.4 Hz, 1H), 7.02-6.97 (m, 2H), 4.13-4.04 (m, 1H), 3.87-3.78 (m, 2H), 3.20-3.01 (m,
2H), 1.44 (d, J = 8.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 172.1, 147.43 (d, J = 8.0 Hz), 143.4,
140.89 (d, J = 4.0 Hz), 139.7, 134.4 (d, J = 12.0 Hz), 133.3, 132.3 (d, J = 9.0 Hz), 131.9 (d, J = 2.0 Hz),
131.7, 131.6, 131.5, 131.4, 131.35, 131.2 (d, J = 2.0 Hz) 130.1, 128.9, 128.5, 128.4, 128.36, 128.3,
127.5, 126.7 (d, J = 12.0 Hz), 126.0, 124.5, 123.6, 117.2, 47.8, 45.8, 28.1, 20.3. 31P NMR (162 MHz,
CDCl3) δ 29.1. HRMS (ESI) m/z: [M+H]+ calcd for C35H31NO2P 528.2087; found 528.2086.

2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)pentan-3-one (4s)
The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2t (148.5 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/20) to afford the title compound as colorless oil (59.7 mg, 47%
yield). 1H NMR (400 MHz, CDCl3) δ 7.42-7.38 (m, 1H), 7.33-7.27 (m, 9H), 7.24-7.16 (m, 5H),
7.10-7.08 (m, 1H), 7.02-6.99 (m, 2H), 3.54 (q, J = 8.0 Hz, 1H), 2.31-2.17 (m, 2H), 1.24 (d, J = 8.0 Hz,
3H), 0.92 (t, J = 8.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 211.7, 148.0 (d, J = 27.0 Hz), 142.5 (d, J
= 6.0 Hz), 140.2, 137.7 (d, J = 13.0 Hz), 137.6 (d, J = 9.0 Hz), 136.0 (d, J = 14.0 Hz), 134.3, 134.2,
134.2, 134.1, 134.0, 131.8 (d, J = 2.0 Hz), 131.7 (d, J = 1.0 Hz), 130.3 (d, J = 5.0 Hz), 129.8 (d, J = 4.0
Hz), 128.9, 128.7 (d, J = 1.0 Hz), 128.6, 128.6, 128.5, 128.5, 128.4, 127.7, 126.6, 52.7, 34.3, 17.2, 8.1.
31P NMR (162 MHz, CDCl3) δ -12.9. HRMS (ESI) m/z: [M+H]+ calcd for C29H28OP 423.1872; found
423.1868.

(3'-(octan-2-yl)-[1,1'-biphenyl]-2-yl)diphenylphosphane (4t)
The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), 2u (173.7 mg, 0.9 mmol, 3
equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09
mmol) in toluene (2.0 mL) was stirred at 160℃ in heating mantle for 24 h under an atmosphere of
argon. At ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short
pad of silica gel. The solvent was removed in vacuo and the residue was purified by prepared column

S30
chromatography (Rf = 0.6, hexane) to afford the title compound as colorless oil (37.9 mg, 28% yield).
1H NMR (400 MHz, CDCl3) δ 7.42-7.38 (m, 1H), 7.38-7.34 (m, 1H), 7.31-7.28 (m, 6H), 7.25-7.20 (m,
6H), 7.10 (t, J = 8.0 Hz, 2H), 7.05-7.02 (m, 1H), 6.93 (d, J = 2.0 Hz, 1H), 2.54-2.45 (m, 1H), 1.41-1.31
(m, 2H), 1.27-1.20 (m, 8H), 1.05 (d, J = 8.0 Hz, 3H), 0.78 (t, J = 8.0 Hz, 3H). 13C NMR (100 MHz,
CDCl3) δ 147.6 (d, J = 28.0 Hz), 146.1, 140.5 (d, J = 6.0 Hz), 136.9 (d, J = 5.0 Hz), 136.8 (d, J = 5.0
Hz), 134.7 (d, J = 14.0 Hz), 133.2, 133.0, 132.8, 129.08 (d, J = 5.0 Hz), 127.6, 127.54, 127.49, 127.34,
127.32, 127.25, 126.5, 126.2, 125.8 (d, J = 3.0 Hz), 125.0, 38.7, 37.2, 30.8, 28.4, 26.6, 21.7, 20.8, 13.1.
31P NMR (162 MHz, CDCl3) δ -13.2. HRMS (ESI) m/z: [M+H]+ calcd for C30H32P 451.2549; found
451.2540.

(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)-2,3,4,7,8,9,10,11,12,13,1
4,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl
2-(2'-(diphenylphosphoryl)-[1,1'-biphenyl]-3-yl)propanoate (4u)
The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), corresponding alkyl bromine
(313.0 mg, 0.6 mmol, 3 equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol),
2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09 mmol) in toluene (2.0 mL) was stirred at 140℃ in
heating mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was
added, and the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo
and the residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/10), then
oxidized by hydrogen peroxide to afford the title compound as a white solid (128.9 mg, 81% yield). 1H
NMR (400 MHz, CDCl3) δ 7.62-7.52 (m, 5H), 7.46-7.28 (m, 9H), 7.19-7.15 (m, 1H), 7.14 (s, 1H),
7.04-6.97 (m, 2H), 5.35 (dd, J = 12.0, 4.0 Hz, 1H), 4.63-4.53 (m, 1H), 3.50 (q, J = 8.0 Hz, 1H), 2.30 (d,
J = 8.0 Hz, 1H), 2.22 (d, J = 8.0 Hz, 1H), 2.05-1.76 (m, 5H), 1.73 (d, J = 4.0 Hz, 2H), 1.63-1.41 (m,
7H), 1.34 (d, J = 8.0 Hz, 3H), 1.28-0.93 (m, 15H), 0.91 (d, J = 8.0 Hz, 3H), 0.86 (dd, J = 6.8, 2.0 Hz,
6H), 0.67 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 173.9, 147.48 (d, J = 9.0 Hz), 140.5 (d, J = 4.0 Hz),
139.7 (d, J = 2.0 Hz), 139.4, 134.2 (d, J = 12.0 Hz), 133.5 (d, J = 5.0 Hz), 132.5 (d, J = 5.0 Hz), 132.13,
132.07, 132.0,131.8 (d, J = 22.0 Hz), 131.7, 131.6, 131.5, 131.1 (d, J = 3.0 Hz), 129.5, 129.0, 128.1 (d,
J = 2.0 Hz), 128.0 (d, J = 2.0 Hz), 127.5, 126.7, 126.6, 126.0, 122.6 (d, J = 3.0 Hz), 74.1, 56.7, 56.1,
50.0, 45.4, 42.3, 39.7, 39.5, 38.0, 37.0, 36.6, 36.2, 35.8, 31.9, 28.2, 28.0, 27.6, 24.3, 23.8, 22.8, 22.6,
21.0, 19.3, 18.7, 18.6, 11.9. 31P NMR (162 MHz, CDCl3) δ 28.0. HRMS (ESI) m/z: [M+H]+ calcd for
C54H68O3P 795.4901; found 795.4891.

S31
(1S,2R,5S)-2-isopropyl-5-methylcyclohexyl
2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (4v)
The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv) corresponding alkyl bromine
(174.7 mg, 0.6 mmol, 3 equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol),
2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09 mmol) in toluene (2.0 mL) was stirred at 140℃ in
heating mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was
added, and the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo
and the residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to
afford the title compound as a white solid (78.0 mg, 71% yield). 1H NMR (400 MHz, CDCl3) δ
7.40-7.36 (m, 1H), 7.32-7.20 (m, 14H), 7.12-7.10 (m, 1H), 7.06-6.97 (m, 2H), 4.65-4.54 (m, 1H),
3.53-3.46 (m, 1H), 2.00-1.59 (m, 4H), 1.53-1.39 (m, 2H), 1.30 (dd, J = 7.2, 2.8 Hz, 4H), 0.92-0.79 (m,
7H), 0.70 (dd, J = 6.8, 4.8 Hz, 3H), 0.52 (d, J = 4.0 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 174.0 (d, J
= 11.0 Hz), 148.1 (d, J = 28.0 Hz), 141.9 (d, J = 3.0 Hz), 141.8 (d, J = 3.0 Hz), 139.9 (d, J = 14.0 Hz),
138.0, 137.9 (d, J = 3.0 Hz), 137.7 (d, J = 4.0 Hz), 137.6, 135.9 (d, J = 15.0 Hz), 134.1 (d, J = 3.0 Hz),
133.9 (d, J = 3.0 Hz), 130.14 (d, J = 2.0 Hz), 130.09 (d, J = 2.0 Hz), 129.2 (d, J = 4.0 Hz), 129.1 (d, J =
3.0 Hz), 128.6, 128.5, 128.45 (d, J = 1.0 Hz), 128.4, 128.37, 128.3, 128.2 (d, J = 3.0 Hz) 127.7, 127.4,
126.3 (d, J = 2.0 Hz),74.42, 74.35, 47.1, 46.9, 45.8, 45.6, 40.9, 40.5, 34.28, 34.26, 31.4, 31.3, 26.2, 25.7,
23.4, 23.2, 22.1, 22.01, 20.8, 20.7, 18.2, 18.0, 16.2, 15.9. 31P NMR (162 MHz, CDCl3) δ -13.3. HRMS
(ESI) m/z: [M+H]+ calcd for C37H42O2P 549.2917; found 549.2902.

(8R,9S,13S,14S)-13-methyl-17-oxo-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenant
hren-3-yl 2-(2'-(diphenylphosphino)-[1,1'-biphenyl]-3-yl)propanoate (4w)
The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), corresponding alkyl bromine
(243.2 mg, 0.6 mmol, 3 equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol),
2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09 mmol) in toluene (2.0 mL) was stirred at 140℃ in
heating mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was
added, and the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo
and the residue was purified by prepared column chromatography (Rf = 0.6, EA/hexane = 1/20) to
afford the title compound as a white solid (70.3 mg, 53% yield). 1H NMR (400 MHz, CDCl3) δ

S32
7.42-7.37 (m, 1H), 7.31-7.27 (m, 9H), 7.24-7.19 (m, 5H), 7.18-7.13 (m, 2H), 7.05 (dd, J = 7.2, 3.2 Hz,
1H), 6.87-6.74 (m, 3H), 3.76 (q, J = 7.2 Hz, 1H), 2.92-2.82 (m, 3H), 2.48 (dd, J = 8.4, 4.2 Hz, 1H),
2.39-2.37 (m, 1H), 2.05-2.02 (m, 1H), 2.01-1.92 (m, 3H), 1.66-1.57 (m, 3H), 1.57-1.46 (m, 6H), 1.43 (d,
J = 7.2 Hz, 3H), 0.91-0.89 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 173.2, 169.9, 148.8, 148.6, 147.9 (d,
J = 28.0 Hz), 147.7, 142.1 (d, J = 6.0 Hz), 139.2, 137.9, 137.2, 134.1, 134.0, 133.9, 130.1 (d, J = 5.0
Hz), 129.3 (d, J = 4.0 Hz), 128.7, 128.5 (d, J = 3.0 Hz), 128.4 (d, J = 7.0 Hz), 128.1, 127.5, 126.3 (d, J
= 3.0 Hz), 121.5, 118.6, 50.4, 48.0, 45.5, 44.1, 38.0, 35.9, 31.6, 29.4, 26.3, 25.8, 21.6, 13.8. 31P NMR
(162 MHz, CDCl3) δ -13.1. HRMS (ESI) m/z: [M+H]+ calcd for C45H44O3P 663.3023; found 663.3034.

1-((3aR,6S,7aS)-8,8-dimethyl-2,2-dioxidohexahydro-1H-3a,6-methanobenzo[c]isothiazol-1-yl)-2-(2
'-(diphenylphosphoryl)-[1,1'-biphenyl]-3-yl)propan-1-one (4x)
The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), corresponding alkyl bromine
(210.0 mg, 0.6 mmol, 3 equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol),
2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09 mmol) in toluene (2.0 mL) was stirred at 140℃ in
heating mantle for 24 h under an atmosphere of argon. At ambient temperature, EtOAc (15 mL) was
added, and the mixture was filtered through a short pad of silica gel. The solvent was removed in vacuo
and the residue was purified by prepared column chromatography (Rf = 0.1, EA/hexane = 1/3), then
oxidized by hydrogen peroxide to afford the title compound as a white solid (62.4 mg, 50% yield). 1H
NMR (400 MHz, CDCl3) δ 7.64-7.57 (m, 2H), 7.54-7.48 (m, 3H), 7.46-7.31 (m, 8H), 7.30-7.24 (m,
4H), 7.09-7.02 (m, 3H), 4.13 (q, J = 8.0 Hz, 1H), 3.87 (dd, J = 8.0, 4.0 Hz, 1H), 3.44 (d, J = 4.0 Hz, 2H),
2.02 (s, 1H), 1.97-1.71 (m, 6H), 1.33 (d, J = 8.0 Hz, 3H), 0.90 (s, 3H), 0.86 (s, 3H). 13C NMR (100
MHz, CDCl3) δ 173.6, 147.5 (d, J = 9.0 Hz), 140.5 (d, J = 4.0 Hz), 138.4, 134.1 (d, J = 12.0 Hz), 133.5
(d, J = 8.0 Hz), 132.5 (d, J = 8.0 Hz), 132.1, 132.0, 131.9, 131.7, 131.6, 131.5, 131.4, 131.2 (d, J = 3.0
Hz), 131.1 (d, J = 3.0 Hz), 130.1, 129.7, 129.3, 128.2, 128.1, 128.0, 127.4, 127.1, 126.6, 126.5, 126.3,
65.0, 53.2, 48.3, 47.6, 45.3, 44.6, 38.1, 32.7, 26.4, 20.5, 19.8, 17.6. 31P NMR (162 MHz, CDCl3) δ 27.9.
HRMS (ESI) m/z: [M+H]+ calcd for C37H39NO4PS 624.2332; found 624.2326.

(R)-2,5,7,8-tetramethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chroman-6-yl
2-(2'-(diphenylphosphoryl)-[1,1'-biphenyl]-3-yl)propanoate (4y)

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The general procedure was applied to 1a (101.4 mg, 0.3 mmol, 1 equiv), corresponding alkyl bromine
(339.4 mg, 0.6 mmol, 3 equiv), [RuCl2(p-cymene)]2 (9.2 mg, 0.015 mmol),
2,2,6,6-tetramethylheptane-3,5-dione (16.6 mg, 0.09 mmol) in toluene (2.0 mL)1a (67.6mg, 0.2 mmol,
1 equiv), corresponding alkyl bromine (339.4mg, 0.6 mmol, 3 equiv), [RuCl2(p-cymene)]2 (6.1mg, 5.0
mol%), 2,2,6,6-tetramethylheptane-3,5-dione (11.0mg, 30 mol%), KOAc (39.2mg, 0.4 mmol, 2.0 equiv)
in toluene (2.0 mL) was stirred at 140℃ in heating mantle for 24 h under an atmosphere of argon. At
ambient temperature, EtOAc (15 mL) was added, and the mixture was filtered through a short pad of
silica gel. The solvent was removed in vacuo and the residue was purified by prepared column
chromatography (Rf = 0.6, EA/hexane = 1/20), then oxidized by hydrogen peroxide to afford the title
compound as a white solid (127.6 mg, 76% yield). 1H NMR (400 MHz, CDCl3) δ 7.62-7.54 (m, 5H),
7.45-7.40 (m, 1H), 7.39-7.28 (m, 8H), 7.24 (d, J = 12.0 Hz, 2H), 7.17 (d, J = 8.0 Hz, 1H), 7.07 (t, J =
8.0 Hz, 1H), 3.82 (q, J = 8.0 Hz, 1H), 2.53 (s, 2H), 2.04 (s, 3H), 1.92-1.65 (m, 9H), 1.55-1.48 (m, 6H),
1.36-1.23 (m, 12H), 1.17-0.98 (m, 8H), 0.85 (m, 12H). 13C NMR (100 MHz, CDCl3) δ 172.9, 149.3,
147.45 (d, J = 8.0 Hz), 140.7 (d, J = 4.0 Hz), 140.4, 138.7, 134.2 (d, J = 12.0 Hz), 133.6 (d, J = 7.0 Hz),
132.5 (d, J = 8.0 Hz), 132.2, 132.1, 132.0, 131.8 (d, J = 2.0 Hz), 131.7, 131.6 (d, J = 1.0 Hz), 131.5,
131.2 (d, J = 2.0 Hz), 131.1, 129.8, 129.4, 128.2 (d, J = 2.0 Hz), 128.1 (d, J = 2.0 Hz), 127.6, 126.8,
126.6, 126.5 122.9, 117.3, 75.0, 45.3, 39.4, 37.5, 37.3, 32.8, 32.7, 28.0, 24.8, 24.5, 22.8, 22.7, 21.0, 20.6,
19.8, 19.7, 18.2, 11.8. 31P NMR (162 MHz, CDCl3) δ 28.0. HRMS (ESI) m/z: [M+H]+ calcd for
C56H72O4P 839.5163; found 839.5158.

ethyl 3-(2'-(diphenylphosphino)-5-(1-ethoxy-1-oxopropan-2-yl)-[1,1'-biphenyl]-2-yl)propanoate
(8)[2]
Dr = 1:1. 1H NMR (400 MHz, CDCl3) δ 7.38 (t, J = 8.0 Hz, 2H), 7.29 (m, 13H), 7.22-7.13 (m, 15H),
7.07-7.03 (m, 2H), 6.65 (s, 1H), 6.57 (s, 1H), 4.10-3.97 (m, 8H), 3.41 (q, J = 8.0 Hz, 1H), 3.26 (q, J =
8.0 Hz, 1H), 2.82-2.70 (m, 4H), 2.53-2.44 (m, 4H), 1.23-1.15 (m, 15H), 1.01 (d, J = 8.0 Hz, 3H). 13C

NMR (100 MHz, CDCl3) δ 174.6, 174.5, 173.1, 146.8 (d, J = 17.0 Hz), 146.5 (d, J = 16.0 Hz), 141.1 (d,
J = 7.0 Hz), 140.8 (d, J = 7.0 Hz), 137.7, 137.6, 137.55, 137.47, 137.4, 137.3, 137.0, 136.9, 136.88,
136.83, 136.79, 136.72, 136.68, 136.57, 134.1, 134.0, 133.9, 133.8, 133.78, 133.7, 133.6, 130.8 (d, J =
3.0 Hz), 130.0 (d, J = 6.0 Hz), 129.6 (d, J = 3.0 Hz), 128.71, 128.67, 128.63, 128.6, 128.5, 128.4, 128.3,
128.2, 127.7 (d, J = 3.0 Hz), 127.5, 126.1, 60.6 (d, J = 3.0 Hz), 60.3, 44.9 (d, J = 7.0 Hz), 34.9,
28.3-28.2 (m), 18.4, 17.9, 14.2 (d, J = 5.0 Hz). 31P NMR (162 MHz, CDCl3) δ -13.6, -13.9. HRMS
(ESI) m/z: [M+H]+ calcd for C34H36O4P 539.2346; found 539.2335.

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ethyl 2-(2''-(diphenylphosphino)-2-methoxy-[1,1':2',1''-terphenyl]-4'-yl)propanoate (9) [3]
dr = 1:1. 1H NMR (400 MHz, CDCl3) δ 7.33 (s, 1H), 7.32-7.27 (m, 8H), 7.19 (m, 15H), 7.15-7.05 (m,
5H), 6.94-6.86 (m, 7H), 6.81-6.74 (m, 3H), 6.70 (dd, J = 8.0, 4.0 Hz, 2H), 4.13-3.98 (m, 4H), 3.60 (d, J
= 4.0 Hz, 6H), 3.51 (q, J = 8.0 Hz, 1H), 3.40 (q, J = 8.0 Hz, 1H), 1.32 (d, J = 8.0 Hz, 3H), 1.22-1.13 (m,
9H). 13C NMR (100 MHz, CDCl3) δ 174.6, 174.5, 156.5, 148.2 (d, J = 6.0 Hz), 147.9 (d, J = 6.0 Hz),
141.4 (d, J = 7.0 Hz), 141.3 (d, J = 7.0 Hz), 138.9, 138.8, 138.7, 138.6, 138.5, 138.3, 136.4 (d, J = 3.0
Hz), 136.1, 136.0 (d, J = 2.0 Hz), 135.9, 134.0, 133.8, 133.2 (d, J = 1.0 Hz), 133.0, 132.41-132.35 (m),
130.8, 130.7, 130.6, 130.1 (d, J = 5.0 Hz), 129.8 (d, J = 4.0 Hz), 128.5, 128.4, 128.33,128.28, 128.1 (d,
J = 6.0 Hz), 127.9, 127.8, 127.1, 126.9, 125.9, 119.9 (d, J = 2.0 Hz), 110.3, 60.6, 55.1 (d, J = 3.0 Hz),
45.1 (d, J = 6.0 Hz), 18.5, 18.0, 14.2. 31P NMR (162 MHz, CDCl3) δ -13.9. HRMS (ESI) m/z: [M+H]+
calcd for C36H34O3P 545.2240; found 545.2231.

4. References

[1] Bandari, R.; Hoche, T.; Prager, A.; Dirnberger, K.; Buchmeiser, M. R. Chem - Eur. J. 2010, 16,
4650-4658.
[2] Li, J.-W.; Wang, L.-N.; Li, M.; Tang, P.-T.; Zhang, N.-J.; Li, T.; Luo, X.-P.; Kurmoo, M.; Liu,
Y.-J.; Zeng, M.-H. Org. Lett. 2020, 22, 1331-1335.
[3] Li, J.-W.; Wang, L.-N.; Li, M.; Tang, P.-T.; Luo, X.-P.; Kurmoo, M.; Liu, Y.-J.; Zeng, M.-H. Org.
Lett. 2019, 21, 2885-2889.

5. NMR spectra

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