Tetrahedron 75 (2019) 1166e1170

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Tetrahedron
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Functionalized pyrroles from vinylaziridines and alkynes via rhodium-

catalyzed domino ring-opening cyclization followed by C]C bond
migration
Shu-Hao Wan, Shiuh-Tzung Liu*
Department of Chemistry, National Taiwan University, Taipei, 106, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: Rhodium(I)-catalyzed intermolecular cycloadditions of alkynes with vinyl aziridines bearing a conju-
Received 23 October 2018 gated carbonyl group in the olefin moiety followed by the double migration resulted in the formation of
Received in revised form pyrrole derivatives in a one pot fashion.
6 January 2019
© 2019 Elsevier Ltd. All rights reserved.
Accepted 11 January 2019
Available online 14 January 2019

Keywords:
Cycloaddition
Aziridine
Pyrrole
Isomerization
Rhodium

1. Introduction 2. Results and discussion

Transition-metal catalysis toward the development of effective The starting substrate 5 in a mixture of E/Z forms was obtained
methods for carbon
carbon and carbon
heteroatom bond for- according to the reported method [1c]. Reaction of E/Z-5 with
mation have been received much attention in particular for those of phenylacetylene in the presence of [Rh(NBD)2]BF4 in 1,2-
the synthesis of heterocycles. Quite a number of readily available dichloroethane at ambient temperature proceeded smoothly. By
compounds have been prepared in this regard. Among them, vinyl-
substituted aziridines 1 are known as valuable substrates for
transition-metal-catalyzed [3 þ 2], [3 þ 3], [3 þ 4] or [5 þ 2]
annulation reactions with alkynes for five, six or seven membered
heterocycles, respectively [1e5]. In the [3 þ 2] annulations, vinyl-
aziridine acts as a three atom component for the five-member
ring leaving the vinyl group unreacted, rendering the vinyl-
dihydropyrrole product 2 (Scheme 1). However, this compound
readily undergoes hydrolysis in the presence of a Lewis acid, giving
geamino ketone 3 [3]. In fact, these two steps leading to 3 can be
carried out in a one-pot fashion. In this context, not much effort has
addressed about the double bond migration leading to the pyrrole
4. Here, we would like to report the preparation of vinyl-
dihydropyrroles via the rhodium catalyzed cycloaddition and the
double bond isomerization reaction leading to the corresponding
pyrroles in a one-pot fashion.

* Corresponding author.
E-mail address: stliu@ntu.edu.tw (S.-T. Liu). Scheme 1. Cycloaddition of vinyl aziridines with alkynes.

https://doi.org/10.1016/j.tet.2019.01.022
0040-4020/© 2019 Elsevier Ltd. All rights reserved.
 S.-H. Wan, S.-T. Liu / Tetrahedron 75 (2019) 1166e1170 1167

monitoring the reaction, we found that the E-isomer was trans- Table 1
formed into dihydropyrrole 6a within 0.5 h, but the Z-isomer Optimization of isomerization of 6a into 7 and 9aa.

remained in the solution. However, upon standing a longer time,

the Z-isomer was eventually converted into 6a, indicating that the E
form is more reactive than the Z isomer. Such a selectivity is similar
to those reported in cycloadditions [1c,1d,6]. The trans configura-
tion in 6a was established by 1H NMR spectroscopy. The observed J
value for Ha and Hb in 6a is 15.7 Hz, which is comparable to those of
the a,b-unsaturated ester in E configuration. Compound 6a was entry Base (amount) t ( C) 7 9a
quite sensitive to water under acidic conditions, as expected, and it 1 iPr2NH (1 eq) 50 85% 15%
readily underwent ring opening reaction to yield the amino ketone 2 Pyrrolidine (1 eq) 50 trace 99%
7 [3]. However, treatment of 6a with a base followed by acid 3 Et3N (1 eq) 50 11% 89%
workup rendered the pyrrole product 9a, indicating that the 4 Pyridine (1 eq) 50 99% trace
5 p-DMAP (1 eq) 50 7% 93%
isomerization of 6a under basic condition could avoid the ring
6 DABCO (1 eq) 50 trace 99%
opening hydrolysis. 7 DABCO (0.5 eq) 50 trace 99%
The isomerization was studied by monitoring the reaction in 8 DABCO (0.2 eq) 50 16% 84%
CDCl3 with 1H-NMR spectroscopy. Upon addition of a base, com- 9 DABCO (0.5 eq) rt 57% 43%
pound 6a was converted into 8a as evidenced by the disappearance 10 None rt 99% trace

of the signal corresponding to Hg and an upfield shift of Ha to a

2.7 ppm with the integration of 2H (Fig. 1a and b). The NOE
experiment showed the interaction between Hε and Hb, not Ha.
Thus, the stereochemistry of compound 8a is established as shown
in Scheme 2 [7]. We also believed that the ester functionality in the
molecule may also assist the double bond migration, presumably
due to the increasing acidity of Hg [8]. Finally, the isomerization
proceeded further to yield the pyrrole 9a by adjusting the medium
to an acidic condition (Fig. 1c). Table 1 summarizes the study of
Fig. 1. Partial 1H NMR spectra of 6a (a), 8a (b) and 9a (c) for comparison.
A sample of 6a (40 mg, 0.10 mmol) in CDCl3 (0.5 mL) was added with base. After
1 h, CF3CO2H (0.15 mmol) was added.
isomerization with various bases. Most organic bases assist this
isomerization, but 1,4-diazabicyclo[2.2.2]octane (DABCO) appears
to be the most efficient one.
With the optimal information, a broad range of substituted
phenylacetylenes were explored as substrates leading to the cor-
responding pyrroles in a one-pot fashion and the results are shown
in Table 2. Various p-substituted phenylacetylene participated well
in the reaction and furnished the corresponding pyrroles in good
yields except nitro and cyano substituents. Common functional
groups such as alkyl, ester, keto, ether and halogens were found
compatible and the desired products were obtained in good yields.
Furthermore, 2,4,6-trimethylphenylacetylene and naph-
thylacetylene underwent the cycloaddition followed by isomeri-
zation to give 9j (62%) and 9k (73%), respectively. Notably, 2,4,6-
trimethylphenylacetylene with sterically distinct substituents
delivered 9j in good yield. The use of p-nitrophenylacetylene as the
substrate provided a complicated mixture of products and the
desired compound 6h was determined by NMR in 11% yield.
However, reaction of 5 with p-cyanophenylacetylene did not give
any desired product, presumably due to the coordination ability of
nitrile group toward the metal center. The reactivity of diphenyla-
cetylene appeared to be poor and the reaction only gave 9l in 19%
by NMR, but acetyl phenylacetylene gave 9m in a reasonable yield.
Unfortunately, alkyl substituted alkynes were not applicable to this
methodology. Under the optimal conditions, reaction of 5 with 1-
pentyne afforded g-aminoketone 10 as the isolated product in
74% (Eqn. (1)). However, reaction of 5 with N-ethynyl-N,4-
dimethyl-benzenesulfonamide, a ynamide substrate, did not pro-
vide the pyrrole product under the standard conditions. In addition,
a benzoyl substituted vinyl aziridine 11 underwent smoothly with
phenyacetylene to yield the cycloadduct 12, and then isomerize to
the pyrrole product 13 (Eqn. (2)). Notably, reaction of 1-[(4-
methylphenyl)sulfonyl]-2-[(1E)-2-phenylethenyl]aziridine, a sub-
strate without an ester functionality, with phenylacetylene gave a
complicated mixture of unidentified products, indicating the ne-
cessity of carbonyl functionality in aziridine components.

(1)

Scheme 2. Cycloaddition followed by isomerization to yield pyrroles.

1168 S.-H. Wan, S.-T. Liu / Tetrahedron 75 (2019) 1166e1170

Table 2
Reaction of various phenylacetylene with 5 leading to pyrrolesa.

3. Summary

We have developed a synthetic method of preparation of func-

(2)
According to the mechanism of rhodium(I)-catalyzed cycload-
dition of aziridines with alkynes proposed by Zhang, reaction
pathway in this work is presented in Fig. 2 [3]. Oxidative ring
opening of aziridine by Rh(I) gives the p-complex I. Upon coordi-
nation of the alkyne molecule followed by the migratory insertion
renders the metallocycle intermediate III, which then undergoes
the reductive elimination to yield the dihydropyrrole product IV.
This initial product can be either hydrolyzed to produce the g-
amino ketone V or isomerized under basic conditions to generate
VI. Aromatization of VI provides the pyrrole product.
tionalized pyrroles via rhodium-catalyzed coupling of vinyl-
aziridines and alkynes followed by double bond migrations in one-
pot fashion. In this work, the double bond migration steps were
investigated in detail, allowing us to understand the nature of
dihydropyrroles. Current research is focused on extending the
rhodium catalyzed coupling of vinylaziridines with other nucleo-
philes under various conditions.
4. Experimental section
Manipulation was performed by using a standard Schlenk
technique under dry nitrogen atmosphere. Solvents were dried
using standard methods and distilled under nitrogen before use.
The rhodium complex [Rh(NBD)2]BF4 [9], methyl 1-[(4-
methylphenyl)sulfonyl]-2-aziridinecarboxylate [10] and the ethy-
nylarenes were prepared by following the reported method. Mass
spectra were recorded with a LCQ Advantage (ESI) Mass Spec-
trometer. NMR spectra were determined with Bruker AvanceIII-400
or DMX-500 FT-NMR spectrometers at room temperature. 1H and
 S.-H. Wan, S.-T. Liu / Tetrahedron 75 (2019) 1166e1170
Fig. 2. Reaction pathway for the cycloaddition and C]C bond migration.
13
C NMR spectra were obtained in CDCl3.
4.1. Preparation of ethyl 1-[(4-methylphenyl)sulfonyl]-2-
aziridineacrylate (5)
To a solution of methyl 1-[(4-methylphenyl)sulfonyl]-2-
aziridinecarboxylate (2.553 g, 10.00 mmol) in CH2Cl2 (30 mL) was
added diisobutylaluminum hydride (1 M, 12.0 mL, 12.0 mmol)
drop-wise at
78  C under N2 atmosphere. The resulting mixture
was kept at ambient temperature and stirred for 2 h. The reaction
was quenched with 1N HCl (50 mL) and Et2O (3  50 mL) was
added for the extraction the crude product. The organic extracts
were combined, dried over anhydrous MgSO4, filtered and
concentrated to give the crude aldehyde, which was used for the
following step without further purification.
To a suspension of NaH (60%, 600 mg, 15.0 mmol) in THF (30 mL)
was added triethyl phosphonoacetate (3.0 mL, 15 mmol) drop-wise
at 0  C under N2 atmosphere. The resulting mixture was stirred at
ambient temperature until no H2 evolution. The freshly prepared
aldehyde in THF (30 mL) was added to the above solution with
stirring. The reaction was monitored by the TLC analysis to confirm
the completion. The solution was washed with a saturated aqueous
solution of NH4Cl (30 mL) and extracted with EtOAc (3  30 mL).
The combined organic layers were dried over anhydrous MgSO4,
filtered and concentrated under reduced pressure. The residue was
chromatographed on silica gel using EtOAc/hexane ¼ 1/4 as the
eluent to give the desired vinyl aziridine 5 as colorless oil with E/
Z > 20/1. (2.245 g, 76% over 2 steps). E/Z > 20/1. E-isomer: 1H NMR
(d, CDCl3): 7.82 (d, 3JHH ¼ 8.1 Hz, 2H, Ts), 7.35 (d, 3JHH ¼ 8.1 Hz, 2H,
Ts), 6.55 (dd, 3JHH ¼ 15.5 Hz, 3JHH ¼ 7.4 Hz, 1H, ¼CH), 6.10 (dd,
3
JHH ¼ 15.5 Hz, 4JHH ¼ 0.7 Hz, 1H, ¼CH), 4.17 (q, 3JHH ¼ 7.1 Hz, 2H, Et),
3.37-3.32 (m, 1H, aziridine), 2.87 (d, 3JHH ¼ 7.1 Hz, 1H, aziridine),
2.45 (s, 3H, Ts), 2.27 (d, 3JHH ¼ 4.2 Hz, 1H, aziridine), 1.26 (t,
3
JHH ¼ 7.1 Hz, 3H, Et). 13C NMR (d, CDCl3): 165.64 (C]O), 145.32 (C),
141.93 (CH), 135.02 (C), 130.20 (CH), 128.27 (CH), 125.70 (CH), 61.08
(CH2), 38.92 (CH), 34.95 (CH2), 22.00 (CH3), 14.49 (CH3), which are
essentially identical to the literature reported [1c].
4.2. General procedure for preparation of pyrroles
To a solution of 5 (1 equiv.) and [Rh(NBD)2]BF4 (5 mol%) in 1,2-
DCE (1 mL) was added the alkyne (1.5 equiv.) in 1,2-DCE (1 mL).
The resulting mixture was stirred for 0.5 h. Upon the addition of
1,4-diazabicyclo[2.2.2]octane (0.5 equiv.), the mixture was heated
to 50  C for 1 h. The reaction mixture was then neutralized with
trifluoroacetic acid (1.5 equiv). The solvent was removed under
1169
reduced pressure and the residue was purified by column chro-
matography using CH2Cl2/hexane as the eluent to give the desired
pyrrole 9.
9a. Yellow oil. 51 mg, 64%. 1H NMR (d, CDCl3): 7.40-7.26 (m, 8H,
Ar-H), 7.15 (d, 3JHH ¼ 8.3 Hz, 2H, Ar-H), 6.09 (d, 4JHH ¼ 1.8 Hz, 1H,
pyrrole), 4.19 (q, 3JHH ¼ 7.1 Hz, 2H, Et), 2.82 (t, 3JHH ¼ 7.4 Hz, 2H,
CH2), 2.62 (t, 3JHH ¼ 7.4 Hz, 2H, CH2), 2.41 (s, 3H, Ts), 1.31 (t,
3
JHH ¼ 7.1 Hz, 3H, Et). 13C NMR (d, CDCl3): 173.12 (C]O), 144.81 (C),
136.77 (C), 135.94 (C), 131.77 (C), 131.00 (CH), 129.61 (CH), 128.48
(CH), 127.63 (CH), 127.30 (CH), 126.60 (C), 121.17 (CH), 117.13 (CH),
60.75 (CH2), 34.97 (CH2), 22.44 (CH2), 21.86 (CH3), 14.53 (CH3). ESI-
HRMS (TOF): MHþ found 398.1459. C22H24NO4S requires 398.1426.
9b. Yellow oil. 53 mg, 65%. 1H NMR (d, CDCl3): 7.24-7.09 (m, 9H,
Ar-H), 5.99 (d, 4JHH ¼ 2.1 Hz, 1H, pyrrole), 4.13 (q, 3JHH ¼ 7.3 Hz, 2H,
Et), 2.74 (t, 3JHH ¼ 7.6 Hz, 2H, CH2), 2.55 (t, 3JHH ¼ 7.6 Hz, 2H, CH2),
2.39 (s, 3H, CH3), 2.35 (s, 3H, CH3), 1.24 (t, 3JHH ¼ 7.3 Hz, 3H, Et). 13C
NMR (d, CDCl3): 173.15 (C]O), 144.75 (C), 138.35 (C), 136.91 (C),
135.99 (C), 130.84 (CH), 129.59 (CH), 128.87 (C), 128.36 (CH), 127.29
(CH), 126.67 (C), 120.96 (CH), 116.95 (CH), 60.74 (CH2), 34.95 (CH2),
22.43 (CH2), 21.86 (CH3), 21.62 (CH3), 14.51 (CH3). ESI-HRMS (TOF):
MHþ found 412.1599. C23H26NO4S requires 412.1583.
9c. Yellow oil. 57 mg, 67%. 1H NMR (d, CDCl3): 7.31-7.14 (m, 7H,
Ar-H), 6.88 (d, 3JHH ¼ 8.5 Hz, 2H, Ar-H), 6.02 (br, 1H, pyrrole), 4.18 (q,
3
JHH ¼ 7.1 Hz, 2H, Et), 3.90 (s, 3H, OCH3), 2.80 (t, 3JHH ¼ 7.5 Hz, 2H,
CH2), 2.60 (t, 3JHH ¼ 7.5 Hz, 2H, CH2), 2.40 (s, 3H, Ts), 1.30 (t,
3
JHH ¼ 7.1 Hz, 3H, Et). 13C NMR (d, CDCl3): 173.16 (C]O), 159.95 (C),
144.74 (C), 136.54 (C), 136.02 (C), 132.32 (CH), 129.61 (CH), 127.33
(CH), 126.52 (C), 124.13 (C), 120.76 (CH), 116.70 (CH), 113.08 (CH),
60.76 (CH2), 55.58 (CH3), 34.99 (CH2), 22.47 (CH2), 21.88 (CH3), 14.55
(CH3). ESI-HRMS (TOF): MHþ found 428.1548. C23H26NO5S requires
428.1532.
9d. Yellow oil. 54 mg, 63%. 1H NMR (d, CDCl3): 7.29-7.11 (m, 9H,
Ar-H), 6.03 (d, 4JHH ¼ 1.9 Hz, 1H, pyrrole), 4.13 (q, 3JHH ¼ 7.1 Hz, 2H,
Et), 2.75 (t, 3JHH ¼ 7.5 Hz, 2H, CH2), 2.55 (t, 3JHH ¼ 7.5 Hz, 2H, CH2),
2.36 (s, 3H, Ts), 1.24 (t, 3JHH ¼ 7.1 Hz, 3H, Et). 13C NMR (d, CDCl3):
173.05 (C]O), 145.05 (C), 135.87 (C), 135.47 (C), 134.64 (C), 132.19
(CH), 130.26 (C), 129.75 (CH), 127.93 (CH), 127.24 (CH), 126.83 (C),
121.60 (CH), 117.58 (CH), 60.80 (CH2), 34.95 (CH2), 22.40 (CH2), 21.90
(CH3), 14.55 (CH3). ESI-HRMS (TOF): MHþ found 432.1052.
C22H23ClNO4S requires 432.1036.
9e. Yellow oil. 71 mg, 76%. 1H NMR (d, CDCl3): 7.56 (d,
3
JHH ¼ 8.1 Hz, 2H, Ar-H), 7.36 (d, 3JHH ¼ 8.1 Hz, 2H, Ar-H), 7.23-7.21
(m, 3H, Ar-H), 7.11 (d, 3JHH ¼ 8.1 Hz, 2H, Ar-H), 6.09 (d, 4JHH ¼ 1.8 Hz,
1H, pyrrole), 4.13 (q, 3JHH ¼ 7.0 Hz, 2H, Et), 2.76 (t, 3JHH ¼ 7.4 Hz, 2H,
CH2), 2.56 (t, 3JHH ¼ 7.4 Hz, 2H, CH2), 2.36 (s, 3H, Ts), 1.25 (t,
3
JHH ¼ 7.0 Hz, 3H, Et). 13C NMR (d, CDCl3): 172.99 (C]O), 145.21 (C),
1170 S.-H. Wan, S.-T. Liu / Tetrahedron 75 (2019) 1166e1170
135.68 (C), 135.41 (C), 135.23 (C), 131.06 (CH), 130.32 (q,
2 3
JCF ¼ 32.1 Hz, C), 129.78 (CH), 127.16 (CH), 127.09 (C), 124.62 (q,
3
JCF ¼ 3.6 Hz, CH), 124.44 (q, 1JCF ¼ 274.3 Hz, CF3), 122.19 (CH), 118.30
(CH), 60.80 (CH2), 34.88 (CH2), 22.33 (CH2), 21.86 (CH3), 14.52 (CH3).
19
F NMR (d, CDCl3): -62.56 (s, 3F, CF3). ESI-HRMS (TOF): MHþ found
466.1316. C23H23F3NO4S requires 466.1300.
9f. Yellow oil. 66 mg, 75%. 1H NMR (d, CDCl3): 7.88 (d,
3
JHH ¼ 8.4 Hz, 2H, Ar-H), 7.35 (d, 3JHH ¼ 8.4 Hz, 2H, Ar-H), 7.21-7.19
(m, 3H, Ar-H), 7.09 (d, 3JHH ¼ 8.1 Hz, 2H, Ar-H), 6.09 (d, 4JHH ¼ 1.8 Hz,
1H, pyrrole), 4.10 (q, 3JHH ¼ 7.0 Hz, 2H, Et), 2.73 (t, 3JHH ¼ 7.7 Hz, 2H,
CH2), 2.61 (s, 3H, CH3), 2.53 (t, 3JHH ¼ 7.7 Hz, 2H, CH2), 2.33 (s, 3H,
Ts), 1.21 (t, 3JHH ¼ 7.0 Hz, 3H, Et). 13C NMR (d, CDCl3): 197.98 (C]O),
172.89 (C]O), 145.10 (C), 136.57 (C), 136.46 (C), 135.77 (C), 135.62
(C), 130.74 (CH), 129.72 (CH), 127.66 (CH), 127.29 (C), 127.04 (CH),
122.41 (CH), 118.44 (CH), 60.70 (CH2), 34.80 (CH2), 26.90 (CH3),
22.26 (CH2), 21.80 (CH3), 14.46 (CH3). ESI-HRMS (TOF): MHþ found
440.1532. C24H26NO5S requires 440.1532.
9g. Yellow oil. 64 mg, 68%. 1H NMR (d, CDCl3): 7.98 (d,
3
JHH ¼ 8.5 Hz, 2H, Ar-H), 7.32 (d, 3JHH ¼ 8.5 Hz, 2H, Ar-H), 7.22-7.20
(m, 3H, Ar-H), 7.09 (d, 3JHH ¼ 8.5 Hz, 2H, Ar-H), 6.09 (d, 4JHH ¼ 2.1 Hz,
1H, pyrrole), 4.39 (q, 3JHH ¼ 7.1 Hz, 2H, Et), 4.12 (q, 3JHH ¼ 7.1 Hz, 2H,
Et), 2.74 (t, 3JHH ¼ 7.8 Hz, 2H, CH2), 2.54 (t, 3JHH ¼ 7.8 Hz, 2H, CH2),
2.34 (s, 3H, Ts), 1.41 (t, 3JHH ¼ 7.1 Hz, 3H, Et), 1.23 (t, 3JHH ¼ 7.1 Hz, 3H,
Et). 13C NMR (d, CDCl3): 172.98 (C]O), 166.68 (C]O), 145.08 (C),
136.23 (C), 135.89 (C), 135.71 (C), 130.63 (CH), 130.21 (C), 129.74
(CH), 128.89 (CH), 127.14 (CH), 122.26 (CH), 118.24 (CH), 61.35 (CH2),
60.76 (CH2), 34.89 (CH2), 22.34 (CH2), 21.86 (CH3), 14.64 (CH3), 14.52
(CH3). ESI-HRMS (TOF): MHþ found 470.1638. C25H28NO6S requires
470.1637.
9j. Yellow oil. 55 mg, 62%. 1H NMR (d, CDCl3): 7.30-7.27 (m, 3H,
Ts, pyrrole), 7.14 (d, 3JHH ¼ 7.8 Hz, 2H, Ts), 6.80 (s, 2H, mesityl), 5.88
(d, 4JHH ¼ 2.1 Hz, 1H, pyrrole), 4.14 (q, 3JHH ¼ 7.1 Hz, 2H, Et), 2.81 (t,
3
JHH ¼ 7.5 Hz, 2H, CH2), 2.59 (t, 3JHH ¼ 7.5 Hz, 2H, CH2), 2.39 (s, 3H,
CH3), 2.32 (s, 3H, CH3), 1.66 (s, 6H, CH3), 1.25 (t, 3JHH ¼ 7.1 Hz, 3H, Et).
13
C NMR (d, CDCl3): 173.24 (C]O), 144.90 (C), 140.06 (C), 138.76 (C),
136.00 (C), 132.80 (C), 129.67 (CH), 128.17 (CH), 127.84 (CH), 125.34
(C), 118.99 (CH), 115.72 (CH), 60.70 (CH2), 35.28 (CH2), 22.67 (CH2),
21.90 (CH3), 21.53 (CH3), 20.49 (CH3), 14.57 (CH3). ESI-HRMS (TOF):
MHþ found 440.1876. C25H30NO4S requires 440.1896.
9k. Yellow oil. 65 mg, 73%. 1H NMR (d, CDCl3): 7.87-6.82 (12H,
Ar-H), 6.14 (s, 1H, pyrrole), 4.16 (q, 3JHH ¼ 7.1 Hz, 2H, Et), 2.86 (t,
3 [2] (a) T. Li, G. Zhang, J. Guo, S. Wang, X. Leng, Y. Chen, Organometallics 35 (2016)
JHH ¼ 7.5 Hz, 2H, CH2), 2.64 (t, 3JHH ¼ 7.5 Hz, 2H, CH2), 2.21 (s, 3H,
Ts), 1.27 (t, 3JHH ¼ 7.1 Hz, 3H, Et). 13C NMR (d, CDCl3): 173.18 (C]O),
144.63 (C), 135.46 (C), 133.93 (C), 133.22 (C), 132.60 (C), 130.63 (CH),
129.43 (CH), 129.35 (CH), 128.97 (C), 128.01 (CH), 127.49 (CH),
126.09 (CH), 125.64 (CH), 125.55 (C), 125.48 (CH), 124.69 (CH),
119.96 (CH), 117.73 (CH), 60.74 (CH2), 35.14 (CH2), 22.56 (CH2), 21.67
(CH3), 14.55 (CH3). ESI-HRMS (TOF): MHþ found 448.1610.
C26H26NO4S requires 448.1583.
9m. Yellow oil. 50 mg, 57%. 1H NMR (d, CDCl3): 7.44 (t,
3 (h) C.-Z. Zhu, J.-J. Feng, J. Zhang, Chem. Commun. 54 (2018) 2401e2404;
JHH ¼ 7.7 Hz, 1H, Ar-H), 7.32-7.28 (m, 3H, Ar-H), 7.16 (d,
3
JHH ¼ 8.6 Hz, 2H, Ar-H), 7.11 (d, 3JHH ¼ 8.6 Hz, 2H, Ar-H), 7.05 (d,
3
JHH ¼ 7.1 Hz, 2H, Ar-H), 4.15 (q, 3JHH ¼ 7.1 Hz, 2H, Et), 3.00 (t,
3 138 (2016) 2178e2181.
JHH ¼ 7.4 Hz, 2H, CH2), 2.62 (t, 3JHH ¼ 7.4 Hz, 2H, CH2), 2.38 (s, 3H,
Ts), 1.65 (s, 3H, CH3), 1.27 (t, 3JHH ¼ 7.1 Hz, 3H, Et). 13C NMR (d,
CDCl3): 197.06 (C]O), 173.43 (C]O), 145.64 (C), 138.16 (C), 135.52
(C), 132.22 (CH), 130.46 (C), 129.93 (CH), 129.89 (CH), 128.06 (CH),
127.86 (CH), 125.76 (C), 120.53 (CH), 60.67 (CH2), 34.68 (CH2), 30.78
(CH3), 22.32 (CH2), 21.97 (CH3), 14.62 (CH3). ESI-HRMS (TOF): MHþ
found 440.1544. C24H26NO5S requires 440.1532.
12. Colorless oil. 47 mg, 55%. 1H NMR (d, CDCl3): 7.85 (d,
3
JHH ¼ 7.8 Hz, 2H, Ar-H), 7.60-7.39 (m, 10H, Ar-H), 7.21 (d,
3
JHH ¼ 7.8 Hz, 2H, Ar-H), 6.58 (d, 3JHH ¼ 15.2 Hz, 1H, ¼CH), 6.34 (dd,
JHH ¼ 15.2 Hz, 3JHH ¼ 7.1 Hz, 1H, ¼CH), 5.36 (d, 3JHH ¼ 2.8 Hz,
1H, ¼CH), 4.31 (dd, 2JHH ¼ 13.1 Hz, 3JHH ¼ 9.5 Hz, 1H, CHH), 3.87 (dd,
2
JHH ¼ 13.1 Hz, 3JHH ¼ 6.7 Hz, 1H, CHH), 3.40-3.34 (m, 1H, CH), 2.27
(s, 3H, Ts). 13C NMR (d, CDCl3): 189.79 (C]O), 147.32 (CH), 147.05 (C),
144.75 (C), 137.59 (C), 133.31 (CH), 132.67 (C), 129.93 (CH), 129.51
(CH), 128.91 (CH), 128.77 (CH), 128.35 (CH), 128.30 (CH), 128.21
(CH), 125.88 (CH), 117.42 (CH), 56.52 (CH2), 43.69 (CH), 21.73 (CH3).
ESI-HRMS (TOF): MHþ found 430.1474. C26H24NO3S requires
430.1477.
13. Yellow oil. 1H NMR (d, CDCl3): 7.97 (d, 3JHH ¼ 7.8 Hz, 2H, Ar-
H), 7.57 (t, 3JHH ¼ 7.4 Hz, 1H, Ar-H), 7.47 (t, 3JHH ¼ 7.8 Hz, 2H, Ar-H),
7.35-7.20 (m, 8H, Ar-H), 7.07 (d, 3JHH ¼ 8.1 Hz, 2H, Ar-H), 6.08 (d,
4
JHH ¼ 1.8 Hz, 1H, pyrrole), 3.24 (t, 3JHH ¼ 7.4 Hz, 2H, CH2), 2.88 (t,
3
JHH ¼ 7.4 Hz, 2H, CH2), 2.34 (s, 3H, Ts). 13C NMR (d, CDCl3): 199.01
(C]O), 144.39 (C), 136.77 (C), 136.41 (C), 135.51 (C), 133.03 (CH),
131.40 (C), 130.60 (CH), 129.22 (CH), 128.55 (CH), 128.08 (CH), 127.94
(CH), 127.25 (CH), 126.93 (CH), 126.80 (C), 120.85 (CH), 117.03 (CH),
38.80 (CH2), 21.48 (CH3), 21.08 (CH2). ESI-HRMS (TOF): MHþ found
430.1470. C26H24NO3S requires 430.1477.
Acknowledgments
We thank the Ministry of Science and Technology, Taiwan (Grant
No. MOST106-2113-M-002-018) for the financial support. We also
thank “National Taiwan University Mass Spectrometry-based Pro-
teomics Core Facility” for the measurement of ESI mass data.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2019.01.022.
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