Rhodium-Catalyzed Hydrosilylation Reaction of N-Sulfonyl-1,2,3-triazoles with Triphenylsilane: Access to Diverse Compounds

Article abstract of DOI:10.1002/ejoc.201500455

A highly efficient rhodium-catalyzed hydrosilylation of N-sulfonyl-1,2,3-triazoles has been developed. The protocol uses readily available N-sulfonyl-1,2,3-triazoles and triphenylsilane as starting materials, and the reactions first gave 2-(triphenylsilyl)-2-aryl-N-(arylsulfonyl)ethanimines, the isomerization of which provided (E)-2-(triphenylsilyl)-2-aryl-N-(arylsulfonyl)ethenamines in the presence of triethylamine; the reduction of which with LiAlH₄ led to 2-(triphenylsilyl)-2-aryl-N-(arylsulfonyl)ethanamines. It is worthwhile to note that the obtained products could be converted into indole and arylethylamine derivatives. Therefore, the highly efficient rhodium-catalyzed hydrosilylation method is a valuable strategy for synthesis of diverse compounds.

Full text of DOI:10.1002/ejoc.201500455

FULL PAPER
DOI: 10.1002/ejoc.201500455
Rhodium-Catalyzed Hydrosilylation Reaction of N-Sulfonyl-1,2,3-triazoles with
Triphenylsilane: Access to Diverse Compounds
[
a]
[a]
[a]
[a]
[a]
[a]
Hui Wang, Hongwei Qiao, Hao Zhang, Haijun Yang, Yufen Zhao, and Hua Fu*
Keywords: Synthetic methods / Hydrosilylation / Silanes / Rhodium / Nitrogen heterocycles
A highly efficient rhodium-catalyzed hydrosilylation of N-
sulfonyl-1,2,3-triazoles has been developed. The protocol
uses readily available N-sulfonyl-1,2,3-triazoles and tri-
phenylsilane as starting materials, and the reactions first
4
amine; the reduction of which with LiAlH led to 2-(tri-
phenylsilyl)-2-aryl-N-(arylsulfonyl)ethanamines. It is worth-
while to note that the obtained products could be converted
into indole and arylethylamine derivatives. Therefore, the
highly efficient rhodium-catalyzed hydrosilylation method is
a valuable strategy for synthesis of diverse compounds.
gave
2-(triphenylsilyl)-2-aryl-N-(arylsulfonyl)ethanimines,
the isomerization of which provided (E)-2-(triphenylsilyl)-2-
aryl-N-(arylsulfonyl)ethenamines in the presence of triethyl-
Introduction
and convenient protocol with 100% atom efficiency for the
[
3]
synthesis of vinylsilanes.
Importantly, the resulting
Organosilicon compounds show similar reactivity to organosilicon reagents are versatile building blocks in or-
some organometals and organo-metalloids, such as ganic syntheses, such as the protodesilylation of vinylsilanes
[
4]
organotin, organozinc, and organoboron reagents, and they to produce the corresponding alkene, the Hiyama cross-
provide advantages in terms of low cost, low toxicity, high coupling of vinylsilanes with vinyl and aryl halides,[ and
chemical stability and functional group tolerance. Conse- the Tamao–Fleming oxidation of vinylsilanes to generate
5]
[
6]
quently, organosilicon reagents are often used in the synthe- carbonyl derivatives. Unfortunately, the control of stereo-
sis of biologically active small molecules and complex natu- and regioselectivity is a frequent difficulty encountered in
[
1]
ral products. In particular, vinylsilanes are very attractive the transition-metal-catalyzed hydrosilylation reaction of
scaffolds and valuable compounds in synthetic organic alkynes, and the final outcome depends on the catalysts, the
[
2]
chemistry,
and the transition-metal-catalyzed hydro- alkynes, the silanes, and the reaction conditions, such as
[
7]
silylation reaction of alkynes is the most straightforward solvents and temperature. N-Sulfonyl-1,2,3-triazoles are
Scheme 1. Our strategy for the rhodium-catalyzed hydrosilylation reaction of N-sulfonyl-1,2,3-triazoles and further application.
[
a] Key Laboratory of Bioorganic Phosphorus Chemistry and interesting N-heterocyclic compounds that are readily pre-
Chemical Biology (Ministry of Education), Department of
pared by copper-catalyzed cycloaddition reaction of ter-
Chemistry, Tsinghua University,
[
8]
Beijing 100084, P. R. China
minal alkynes with N-sulfonyl azides, and they can form
α-imino metal carbenes with high reactivity under catalysis
E-mail: fuhua@mail.tsinghua.edu.cn
http://chem.tsinghua.edu.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201500455.
[
9]
by transition metals. Recently, various interesting reac-
tions of N-sulfonyl-1,2,3-triazoles have been developed by
Eur. J. Org. Chem. 2015, 4471–4480
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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H. Wang, H. Qiao, H. Zhang, H. Yang, Y. Zhao, H. Fu
FULL PAPER
Fokin, Gevorgyan, Miura, Murakami, and other research tosylethanimine (IIb) under nitrogen atmosphere. Rh2-
[
9,10]
groups.
To the best of our knowledge, hydrosilylation (Oct) -catalyzed reaction of 1b with triphenylsilane (2a) in
4
reaction of N-sulfonyl-1,2,3-triazoles has not been investi- CHCl at 60 °C for 1 h provided almost quantitative 2-(tri-
3
gated thus far.
phenylsilyl)-2-p-tolyl-N-tosylethanimine (IIba) that was ob-
In this paper, our strategy is as follows (see also tained by crystallization in mixed solvent of CHCl and
3
Scheme 1): copper-catalyzed cycloaddition reaction of read- hexane (Table 1, Entry 1). The structure of IIba was con-
1
13
ily available terminal alkynes and N-sulfonyl azides gives firmed by H, C NMR and mass spectrometry (see Sup-
[
8]
N-sulfonyl-1,2,3-triazoles (1) by using previous methods,
rhodium-catalyzed hydrosilylation reaction of 1 with silane stable under acidic, basic, and neutral aqueous conditions,
2) provides 2-(trialkylsilyl)-2-aryl-N-(arylsulfonyl)ethan- so the following two procedures were carried out (Reactions
porting Information for the details). However, IIba was not
(
imines (II), isomerization of II in the presence of base leads A and B). Triethylamine was added to the resulting solution
to 2-(trialkylsilyl)-2-aryl-N-(arylsulfonyl)ethenamines (3), from reaction of 1b and 2a, after a 3 h-treatment, 2-(trialk-
or reduction of II affords 2-(trialkylsilyl)-2-aryl-N-(arylsulf- ylsilyl)-2-p-tolyl-N-tosylethenamine (3b) was provided in
onyl)ethanamines (4). Transition-metal-catalyzed oxidative 93% yield with complete trans configuration because of
cyclization reaction of 3 yields indole derivatives (5), and high steric hindrance of triphenylsilyl (Reaction A). Re-
desilylation of 4 gives N-sulfonyl-2-arylethylamine (6).
duction of IIba with LiAlH in tetrahydrofuran (THF) at
4
0
°C for 5 min afforded 2-(triphenylsilyl)-2-p-tolyl-N-tosyle-
thanamine (4b) in 98% yield (Reaction B). Other solvents
were screened (Table 1, Entries 2–4), but were inferior to
Results and Discussion
As shown in Table 1, rhodium-catalyzed optimized con- CHCl , yields decreased when the temperature was changed
3
ditions were first investigated through reaction of hydro- (Table 1, Entries 1, 5 and 6). Shortened times led to a lower
silylation of 4-p-tolyl-1-tosyl-1H-1,2,3-triazole (1b) with tri- yield (Table 1, Entries 1, 7 and 8). We attempted other tri-
alkylsilane (2) that leads to 2-(trialkylsilyl)-2-p-tolyl-N- alkylsilanes including dimethylphenylsilane (2b), triethylsi-
Table 1. Optimization of conditions for rhodium-catalyzed hydrosilylation reaction of 4-p-tolyl-1-tosyl-1H-1,2,3-triazole (1b) with trialkyl-
silane (2), which leads to 2-(trialkylsilyl)-2-p-tolyl-N-tosylethanimine (IIb), and synthesis of (E)-2-(trialkylsilyl)-2-p-tolyl-N-tosylethen-
amine (3b) and 2-(trialkylsilyl)-2-p-tolyl-N-tosylethanamine (4b).[
a]
3
4
5
Yield of 3b/4b [%][b]
Entry
R , R , R
Solvent
Temp [°C]
Time [h]
1
2
3
4
5
6
7
8
9
Ph, Ph, Ph
Ph, Ph, Ph
Ph, Ph, Ph
Ph, Ph, Ph
Ph, Ph, Ph
Ph, Ph, Ph
Ph, Ph, Ph
Ph, Ph, Ph
Me, Me, Ph
Et, Et, Et
CHCl
3
60
60
60
60
40
80
60
60
60
60
60
1
1
1
1
1
1
0.5
2
1
1
93:98
81:86
16:21
13:19
10:13
89:96
66:72
93:98
0:0
DCE
PhMe
o-xylene
CHCl
CHCl
CHCl
CHCl
CHCl
CHCl
CHCl
3
3
3
3
3
3
3
10
1
0:0
0:0
1
H, Ph, Ph
1
[
a] Reaction conditions: under nitrogen atmosphere, 4-p-tolyl-1-tosyl-1H-1,2,3-triazole (1b; 0.11 mmol), trialkylsilane (2; 0.1 mmol), cata-
lyst (0.001 mmol), solvent (1.0 mL), temperature (40–80 °C), and time (0.5–2 h) in a sealed Schlenk tube for the first reaction. For
4
Reaction A, triethylamine (0.2 mmol), room temperature (≈ 25 °C), and time (3.0 h); For Reaction B, LiAlH (0.1 mmol), THF (2.0 mL)
at 0 °C for 5 min; Oct = octanoate. DCE = 1,2-dichloroethane. [b] Isolated yield.
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Rhodium-Catalyzed Hydrosilylation of N-Sulfonyl-1,2,3-triazoles
lane (2c), and phenylmethylsilane (2d; Table 1, Entries 9– added to the solution. After 3 h, II transformed into 3 in
11). Unfortunately, no satisfactory results were found. good to excellent yields, and only trans-3 was observed as
Therefore, the optimal conditions are as follows: 1 mol-% a result of steric hindrance by the triphenylsilyl group
1
Rh (Oct) as catalyst, triphenylsilane as the hydrosilylating (Table 2). For substituents R in 1, the substrates that con-
2
4
reagent, CHCl as the solvent at 60 °C under nitrogen at- tain electron-donating groups showed higher reactivity than
3
mosphere for the first step of the reaction (from starting those with weak electron-withdrawing groups, and the sub-
materials to II).
strates with strong electron-withdrawing groups, such as
2
Subsequently, we explored the scope for rhodium-cata- NO2 and CF , gave bad results. For substituents R in
3
lyzed hydrosilylation reaction of N-sulfonyl-1,2,3-triazoles 1, the substrates with aryl provided slightly higher yields
(1) with triphenylsilane (2a) and synthesis of 3. The re- than those with alkyl (3p and 3q). The two-step reac-
sulting solution from reaction of 1 with 2a was cooled to tions from 1 and 2a to 3 were tolerant of some functional
room temperature, and then triethylamine (2 equiv.) was groups including ether (3e and 3n), C–F bond (3f), C–Cl
Table 2. Rhodium-catalyzed hydrosilylation reaction of N-sulfonyl-1,2,3-triazoles (1) with triphenylsilane (2a) and synthesis of 3.[a]
[
a] Conditions from starting materials to II: under nitrogen atmosphere, N-sulfonyl-1,2,3-triazole (1; 0.11 mmol), triphenylsilane (2a;
0
.1 mmol), Rh
2
(Oct)
4
(0.001 mmol), CHCl
3
(1.0 mL), temperature (60 °C), and time (1–3 h). Conditions from II to 3: Et
3
N (0.2 mmol)
at room temperature (≈ 25 °C) for 3 h. [b] Isolated yield.
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H. Wang, H. Qiao, H. Zhang, H. Yang, Y. Zhao, H. Fu
FULL PAPER
bond (3g), C–Br bond (3h), naphthyl (3o) and S-heterocycle were tolerant of various functional groups including ether
3r). (4e–4g and 4n), C–F bond (4h), C–Cl bond (4i and 4o), C–
(
Reaction of 1 with 2a led to II under rhodium-catalysis Br bond (4j and 4q), and CF (4r).
3
that was similar to Table 2. The resulting solution was
A possible mechanism for the rhodium-catalyzed hydro-
cooled, then THF and LiAlH were added to the solution silylation reaction of N-sulfonyl-1,2,3-triazoles (1) with tri-
4
at 0 °C, and the reductive reaction was carried out for 5 min phenylsilane (2a) and synthesis of 3 and 4 is proposed in
at this temperature (Table 3). 2-(Triphenylsilyl)-2-aryl-N- Scheme 2 in accordance with the results above and previous
[
9,10]
(
arylsulfonyl)ethanamines (4) were obtained in excellent work.
Rhodium-catalyzed denitrogenation of 1 leads to
II
yields. The two-step reactions (from starting materials to 4) α-imino Rh carbine (I), and reaction of I with triphenylsi-
Table 3. Rhodium-catalyzed hydrosilylation reaction of N-sulfonyl-1,2,3-triazoles (1) with triphenylsilane (2a) and synthesis of 4.[a]
[
0
a] Conditions from starting materials to II: under nitrogen atmosphere, N-sulfonyl-1,2,3-triazole (1; 0.11 mmol), triphenylsilane (2;
.1 mmol), Rh (Oct) (0.001 mmol), CHCl (1.0 mL), temperature (60 °C), and time (1–6 h). Conditions from II to 4: LiAlH (0.1 mmol),
THF (2.0 mL) at 0 °C for 5 min. [b] Isolated yield.
2
4
3
4
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Rhodium-Catalyzed Hydrosilylation of N-Sulfonyl-1,2,3-triazoles
II
[11]
lane (2a) provides II and frees the Rh catalyst. Isomer-
ization of II in the presence of base (Et N) affords 3, and
3
reduction of II with LiAlH in THF gives 4.
4
Scheme 4. Detriphenylsilylation of 4a and 4b in the presence of
TBAF and NaOH.
Conclusions
We have developed a highly efficient rhodium-catalyzed
hydrosilylation reaction of N-sulfonyl-1,2,3-triazoles for the
first time. Reaction of N-sulfonyl-1,2,3-triazoles with tri-
phenylsilane first produced 2-(triphenylsilyl)-2-aryl-N-(aryl-
Scheme 2. Possible mechanism for the rhodium-catalyzed hydro- sulfonyl)ethanimines, and then they performed the follow-
silylation reaction and synthesis of 3 and 4.
ing two procedures: isomerization in the presence of trieth-
ylamine led to (E)-2-(triphenylsilyl)-2-aryl-N-(arylsulfonyl)-
ethenamines; the reduction with LiAlH4 provided 2-(tri-
phenylsilyl)-2-aryl-N-(arylsulfonyl)ethanamines. It is worth-
while to note that the obtained products with triphenylsilyl
could be converted into some useful compounds. Therefore,
Palladium-catalyzed oxidative cyclization reaction of 3
was investigated by consulting published work.[ As shown
12]
in Scheme 3, Pd(OAc) -catalyzed oxidation of 3a or 3b with
2
Cu(OAc) in the presence of oxygen in toluene provided
2
the highly efficient rhodium-catalyzed hydrosilylation
indole derivatives (5a or 5b) in 72 and 75%, respectively.
method is a valuable strategy for synthesis of diverse com-
pounds.
Experimental Section
General: Chloroform was dried with calcium hydride, and toluene
and THF were dried with sodium. Rhodium(II) octanoate dimer
1
13
was purchased from Accela Chemicals. H NMR and C NMR
spectra were recorded in CDCl with tetramethylsilane as the in-
ternal standard ( H NMR: TMS at δ = 0.00 ppm, CHCl at δ =
3
1
3
1
3
7
3
.26 ppm. C NMR: CDCl at δ = 77.2 ppm).
Synthesis of Compound IIba: A 25 mL Schlenk tube was charged a
magnetic stirrer, and the tube was evacuated and refilled with nitro-
gen three times. 4-(p-Tolyl)-1-tosyl-1H-1,2,3-triazole (1b;
0
.11 mmol, 35 mg), triphenylsilane (2a; 0.1 mmol, 26 mg),
Scheme 3. Palladium-catalyzed oxidative cyclization reaction of 3a
and 3b.
Rh (Oct) (0.001 mmol, 0.8 mg), and CHCl (1.0 mL) were added
2
4
3
to the tube under a nitrogen atmosphere, and the tube was sealed
and the mixture was stirred at 60 °C for 1 h. The resulting solution
was concentrated under reduced pressure, and the residue was crys-
tallized from hexane/ethyl acetate to give desired target product
IIba.
We attempted detriphenylsilylation of 4 in the presence
of tetra-n-butylammonium fluoride (TBAF) and NaOH ac-
cording to known conditions.[ As shown in Scheme 4, the
deprotection of 4a or 4b was successfully performed in
mixed solvent of THF and water at 60 °C, and correspond-
ing arylethylamine derivatives 6a and 6b were obtained in
13]
4
-Methyl-N-[2-(p-tolyl)-2-(triphenylsilyl)ethylidene]benzenesulfon-
1
amide (IIba): Yield 54 mg (99%). Yellow solid; m.p. 95–96 °C. H
NMR (CDCl , 400 MHz): δ = 8.83 (d, J = 6.9 Hz, 1 H), 7.53 (d,
J = 8.2 Hz, 2 H), 7.42–7.34 (m, 3 H), 7.29–7.12 (m, 14 H), 6.96 (d,
J = 7.8 Hz, 2 H), 6.77 (d, J = 7.8 Hz, 2 H), 4.43 (d, J = 6.9 Hz, 1
3
87 and 83% yields, respectively. Therefore, the rhodium-cat-
1
3
alyzed hydrosilylation method provides access to diverse H), 2.40 (s, 3 H), 2.28 (s, 3 H) ppm. C NMR (CDCl , 100 MHz):
3
compounds.
δ = 179.5, 144.0, 136.5, 136.3, 135.3, 131.2, 131.1, 130.3, 129.6,
Eur. J. Org. Chem. 2015, 4471–4480
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H. Wang, H. Qiao, H. Zhang, H. Yang, Y. Zhao, H. Fu
29.4, 129.3, 128.0, 127.8, 47.1, 21.7, 21.1 ppm. HRMS (ESI ): 8.2 Hz, 2 H), 7.34–7.27 (m, 12 H), 7.01 (d, J = 7.8 Hz, 2 H), 6.60
FULL PAPER
1
+
+
calcd. for C34
H
31NNaO
2
SSi [M + Na] 568.1742; found 568.1741.
(d, J = 7.28 Hz, 2 H), 6.59 (d, J = 11.9 Hz, 1 H), 6.49 (d, J =
1
7
1
1
1.9 Hz, 1 H), 2.59 (q, J = 7.8 Hz, 2 H), 2.51 (s, 3 H), 1.21 (t, J =
.8 Hz, 3 H) ppm. C NMR (CDCl , 100 MHz): δ = 144.1, 143.1,
3
General Procedure for Synthesis of Compounds 3 and 4: A 25 mL
Schlenk tube was charged with a magnetic stirrer, and the tube was
evacuated and refilled with nitrogen three times. N-Sulfonyl-1,2,3-
triazole (1; 0.11 mmol), triphenylsilane (2a; 0.1 mmol, 26 mg),
1
3
36.9, 136.5, 134.4, 133.6, 133.4, 130.0, 129.8, 128.77, 128.75,
+
27.9, 127.0, 118.7, 28.6, 21.8, 15.6 ppm. HRMS (ESI ): calcd. for
C
35
H
33NNaO
2
SSi [M + Na]+ 582.1899; found 582.1898.
2 4 3
Rh (Oct) (0.001 mmol, 0.8 mg), and CHCl (1.0 mL) were added
to the tube under a nitrogen atmosphere, and the tube was sealed
and the mixture was stirred at 60 °C until the reaction was complete
(E)-N-[2-(3-Methoxyphenyl)-2-(triphenylsilyl)vinyl]-4-methylbenz-
enesulfonamide (3e): Eluent: hexane/ethyl acetate (7:1), yield 47 mg
(84 %). Off-white solid; m.p. 149–150 °C. H NMR (CDCl3,
1
(TLC). The subsequent two different procedures were performed
as follows:
600 MHz): δ = 7.59 (d, J = 8.2 Hz, 2 H), 7.44–7.39 (m, 3 H), 7.36
(
d, J = 8.2 Hz, 2 H), 7.34–7.27 (m, 12 H), 7.59 (t, J = 7.6 Hz, 1
3
For synthesis of 3: Et N (0.2 mmol, 20 mg) was added to the solu-
tion, and the mixture was stirred at room temperature for 3 h. The
resulting solution was poured into ice/water, and hydrochloric acid
H), 6.71 (dd, J = 8.3, J = 2.0 Hz, 1 H), 6.61 (d, J = 12.4 Hz, 1 H),
6
2
1
1
2
5
.50 (d, J = 11.6 Hz, 1 H), 6.31 (d, J = 7.6 Hz, 1 H), 6.17 (d, J =
1
3
3
.0 Hz, 1 H), 3.48 (s, 3 H), 2.51 (s, 3 H) ppm. C NMR (CDCl ,
(
1 m, 0.5 mL) was added. The solution was stirred and extracted
with CH Cl (3ϫ 2 mL), and the combined organic layer was
washed with brine, dried with anhydrous Na SO , filtered, and con-
50 MHz): δ = 160.1, 144.2, 138.8, 136.9, 139.5, 133.6, 133.3, 130.3,
2
2
30.0, 129.9, 127.9, 127.0, 120.9, 118.5, 113.8, 113.3, 55.0,
2
4
+
+
1.8 ppm. HRMS (ESI ): calcd. for C34
H
31NNaO
3
SSi [M + Na]
centrated. The residue was purified by column chromatography on
silica gel with hexane/ethyl acetate as the eluent to give desired
target product 3.
84.1692; found 584.1696.
(E)-N-[2-(4-Fluorophenyl)-2-(triphenylsilyl)vinyl]-4-methylbenzene-
sulfonamide (3f): Eluent: hexane/ethyl acetate (10:1), yield 49 mg
For synthesis of 4: The resulting solution from reaction of 1 with
1
(
89%). White solid; m.p. 163–164 °C. H NMR (CDCl
3
, 600 MHz):
2
a was cooled, and a suspension of LiAlH
THF (2.0 mL) was added to the solution at 0 °C. The mixture was
stirred at 0 °C for 5 min, and then 3.8 mg of H O was added. The
4
(0.1 mmol, 3.8 mg) in
δ = 7.59 (d, J = 8.2 Hz, 2 H), 7.45–7.40 (m, 3 H), 7.37 (d, J =
.2 Hz, 2 H), 7.34–7.27 (m, 12 H), 6.90–6.85 (m, 2 H), 6.66–6.62
m, 2 H), 6.54 (d, J = 11.7 Hz, 1 H), 6.47 (d, J = 11.7 Hz, 1 H),
8
2
(
2
=
1
solution was warmed to room temperature and filtered. The filtrate
was concentrated, and the residue was purified by column
1
3
.51 (s, 3 H) ppm. C NMR (CDCl
244.2 Hz), 144.3, 136.8, 136.4, 134.1, 133.0, 130.6, 130.5, 130.05,
29.97, 128.0, 126.9, 117.6, 116.3 (d, J = 20.1 Hz), 21.8 ppm.
3
, 150 MHz): δ = 161.9 (d, J
2 3
chromatography on Al O with hexane/ethyl acetate as the eluent
to give desired target product 4.
+
+
HRMS (ESI ): calcd. for C33
found 572.1495.
2
H28FNNaO SSi [M + Na] 572.1492;
(
(
E)-4-Methyl-N-[2-phenyl-2-(triphenylsilyl)vinyl]benzenesulfonamide
3a): Eluent: hexane/ethyl acetate (10:1), yield 47 mg (89%). Yellow
1
(E)-N-[2-(4-Chlorophenyl)-2-(triphenylsilyl)vinyl]-4-methylbenzene-
solid; m.p. 169–170 °C. H NMR (CDCl
3
, 400 MHz): δ = 7.58 (d,
sulfonamide (3g): Eluent: hexane/ethyl acetate (10:1), yield 46 mg
J = 8.4 Hz, 2 H), 7.46–7.37 (m, 3 H), 7.36 (d, J = 8.0 Hz, 2 H),
.34–7.27 (m, 12 H), 7.20–7.14 (m, 3 H), 6.72–6.64 (m, 2 H), 6.50
1
(
81 %). Off-white solid; m.p. 164–165 °C. H NMR (CDCl
3
,
7
13
400 MHz): δ = 7.58 (d, J = 8.2 Hz, 2 H), 7.45–7.40 (m, 3 H), 7.36
d, J = 8.2 Hz, 2 H), 7.32–7.28 (m, 12 H), 7.15 (d, J = 8.2 Hz, 2
H), 6.61 (d, J = 8.2 Hz, 2 H), 6.53 (d, J = 11.9 Hz, 1 H), 6.43 (d,
(s, 2 H), 2.51 (s, 3 H) ppm. C NMR (CDCl
3
, 100 MHz): δ =
(
1
1
C
44.2, 137.4, 136.9, 136.4, 133.7, 133.3, 130.0, 129.9, 129.3, 128.8,
+
27.9, 127.1, 126.9, 118.7, 21.8 ppm. HRMS (ESI ): calcd. for
1
3
+
J = 11.9 Hz, 1 H), 2.51 (s, 3 H) ppm. C NMR (CDCl , 100 MHz):
H
29NNaO
2
SSi [M + Na] 554.1586; found 554.1584.
3
33
δ = 144.3, 136.8, 136.4, 135.9, 134.1, 133.1, 132.9, 130.3, 130.06,
(
E)-4-Methyl-N-[2-(p-tolyl)-2-(triphenylsilyl)vinyl]benzenesulfon-
+
1
30.02, 129.5, 128.0, 126.9, 117.4, 21.8 ppm. HRMS (ESI ): calcd.
amide (3b): Eluent: hexane/ethyl acetate (10:1), yield 51 mg (93%).
SSi [M + Na]+ 588.1196; found 588.1191.
for C33H28ClNNaO
2
1
3
White solid; m.p. 186–187 °C. H NMR (CDCl , 600 MHz): δ =
7
2
7
.58 (d, J = 8.3 Hz, 2 H), 7.44–7.38 (m, 3 H), 7.36 (d, J = 8.3 Hz, (E)-N-[2-(4-Bromophenyl)-2-(triphenylsilyl)vinyl]-4-methylbenzene-
H), 7.34–7.27 (m, 12 H), 6.99 (d, J = 7.8 Hz, 2 H), 6.57 (d, J = sulfonamide (3h): Eluent: hexane/ethyl acetate (10:1), yield 51 mg
1
.8 Hz, 2 H), 6.54 (d, J = 11.7 Hz, 1 H), 6.48 (d, J = 11.7 Hz, 1 (83%). White solid; m.p. 165–166 °C. H NMR (CDCl
3
, 400 MHz):
13
δ = 7.59 (d, J = 8.2 Hz, 2 H), 7.45–7.41 (m, 3 H), 7.36 (d, J =
H), 2.51 (s, 3 H), 2.29 (s, 3 H) ppm. C NMR (CDCl
3
, 150 MHz):
δ = 144.1, 136.9, 136.7, 136.5, 134.2, 133.7, 133.4, 130.0, 129.8,
8.2 Hz, 2 H), 7.35–7.28 (m, 14 H), 6.55 (d, J = 8.2 Hz, 2 H), 6.53
(d, J = 11.9 Hz, 1 H), 6.44 (d, J = 11.9 Hz, 1 H), 2.51 (s, 3 H) ppm.
+
1
28.7, 127.9, 127.0, 118.7, 21.8, 21.2 ppm. HRMS (ESI ): calcd.
+
13C NMR (CDCl , 100 MHz): δ = 144.3, 136.8, 136.4, 134.0, 132.9,
for C34
E)-N-[2-(3,5-Dimethylphenyl)-2-(triphenylsilyl)vinyl]-4-methylbenz-
enesulfonamide (3c): Eluent: hexane/ethyl acetate (10:1), yield
H
31NNaO
2
SSi [M + Na] 568.1742; found 568.1738.
3
1
32.4, 130.6, 130.06, 130.03, 128.0, 126.9, 121.2, 117.3, 21.8 ppm.
(
+
+
HRMS (ESI ): calcd. for C33
32.0691; found 632.0688.
2
H28BrNNaO SSi [M + Na]
6
1
5
3 mg (95 %). White solid; m.p. 161–162 °C. H NMR (CDCl
3
,
4
00 MHz): δ = 7.59 (d, J = 8.2 Hz, 2 H), 7.43–7.38 (m, 3 H), 7.36 (E)-N-[2-Phenyl-2-(triphenylsilyl)vinyl]benzenesulfonamide (3i):
(
d, J = 8.2 Hz, 2 H), 7.34–7.27 (m, 12 H), 6.78 (s, 1 H), 6.54 (d, J Yield 47 mg (91%). Eluent: hexane/ethyl acetate (10:1). White so-
1
=
3
11.9 Hz, 1 H), 6.46 (d, J = 11.9 Hz, 1 H), 6.20 (s, 2 H), 2.51 (s, lid; m.p. 161–162 °C. H NMR (CDCl
H), 2.10 (s, 6 H) ppm. 13C NMR (CDCl
, 100 MHz): δ = 144.1, (m, 3 H), 7.61–7.54 (m, 2 H), 7.44–7.37 (m, 3 H), 7.35–7.27 (m, 12
3
, 400 MHz): δ = 7.74–7.65
3
1
1
38.6, 137.0, 136.9, 136.5, 133.47, 133.44, 129.9, 129.8, 128.7, H), 7.20–7.14 (m, 3 H), 6.70–6.64 (m, 2 H), 6.55 (d, J = 11.9 Hz,
+
13
27.8, 127.0, 126.6, 119.6, 21.8, 21.3 ppm. HRMS (ESI ): calcd.
1 H), 6.51 (d, J = 11.9 Hz, 1 H) ppm. C NMR (CDCl
3
,
+
for C35
H
33NNaO
2
SSi [M + Na] 582.1899; found 582.1896.
100 MHz): δ = 139.8, 137.4, 136.4, 133.5, 133.3, 133.2, 130.0, 129.4,
+
1
29.3, 128.8, 127.9, 127.1, 126.9, 119.3 ppm. HRMS (ESI ): calcd.
(
E)-N-[2-(4-Ethylphenyl)-2-(triphenylsilyl)vinyl]-4-methylbenzene-
for C32 27NNaO
H
2
SSi [M + Na]+ 540.1429; found 540.1433.
sulfonamide (3d): Eluent: hexane/ethyl acetate (10:1), yield 52 mg
1
(
93%). White solid; m.p. 184–185 °C. H NMR (CDCl
3
, 400 MHz):
(E)-N-[2-(p-Tolyl)-2-(triphenylsilyl)vinyl]benzenesulfonamide (3j):
δ = 7.59 (d, J = 8.2 Hz, 2 H), 7.43–7.38 (m, 3 H), 7.36 (d, J =
Eluent: hexane/ethyl acetate (10:1), yield 45 mg (85%). White solid;
4476
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© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 4471–4480

Rhodium-Catalyzed Hydrosilylation of N-Sulfonyl-1,2,3-triazoles
1
m.p. 169–170 °C. H NMR (CDCl
3
, 600 MHz): δ = 7.70 (d, J = 9 H), 7.37–7.30 (m, 6 H), 7.26–7.18 (m, 3 H), 6.90 (d, J = 8.3 Hz,
7
3
6
.6 Hz, 2 H), 7.69–7.66 (m, 1 H), 7.60–7.55 (m, 2 H), 7.44–7.38 (m, 2 H), 6.58 (d, J = 11.7 Hz, 1 H), 6.46 (d, J = 11.7 Hz, 1 H), 2.96
1
3
H), 7.36–7.27 (m, 12 H), 6.98 (d, J = 8.2 Hz, 2 H), 6.57 (s, 1 H),
(s, 2 H) ppm. C NMR (CDCl
3
, 150 MHz): δ = 137.5, 136.5,
1
3
.55 (d, J = 7.6 Hz, 2 H), 6.49 (s, 1 H), 2.29 (s, 3 H) ppm.
, 150 MHz): δ = 139.7, 136.8, 136.4, 134.1, 133.5,
33.3, 130.0, 129.8, 129.4, 128.6, 127.9, 126.9, 119.2, 21.2 ppm.
C
133.2, 133.0, 129.9, 129.4, 129.0, 128.0, 127.2, 117.8, 41.6 ppm.
+
H25NNaO
2
SSi [M + Na]+ 478.1273;
NMR (CDCl
1
HRMS (ESI ): calcd. for C33
found 554.1592.
3
HRMS (ESI ): calcd. for C27
found 478.1268.
+
+
2
H29NNaO SSi [M + Na] 554.1586;
(
(
E)-1-Phenyl-N-[2-phenyl-2-(triphenylsilyl)vinyl]methanesulfonamide
3q): Eluent: hexane/ethyl acetate (7:1), yield 42 mg (79%). Off-
1
(
(
3
E)-N-[2-(4-Ethylphenyl)-2-(triphenylsilyl)vinyl]benzenesulfonamide white solid; m.p. 192–193 °C. H NMR (CDCl , 600 MHz): δ =
3k): Eluent: hexane/ethyl acetate (10:1), yield 48 mg (88%). White
7.45–7.40 (m, 3 H), 7.40–7.27 (m, 17 H), 7.20–7.13 (m, 3 H), 6.80
1
solid; m.p. 147–148 °C. H NMR (CDCl
J = 8.3 Hz, 2 H), 7.69–7.66 (m, 1 H), 7.60–7.55 (m, 2 H), 7.43–
.37 (m, 3 H), 7.33–7.27 (m, 12 H), 7.00 (d, J = 7.6 Hz, 2 H), 6.59 = 137.5, 136.5, 133.5, 133.2, 130.8, 129.8, 129.22, 129.17, 129.09,
3
, 600 MHz): δ = 7.70 (d,
(d, J = 7.6 Hz, 2 H), 6.39 (d, J = 11.7 Hz, 1 H), 6.31 (d, J =
1
3
3
11.7 Hz, 1 H), 4.24 (s, 2 H) ppm. C NMR (CDCl , 150 MHz): δ
7
+
(d, J = 11.0 Hz, 1 H), 6.57 (d, J = 7.6 Hz, 2 H), 6.48 (d, J =
128.98, 128.4, 127.9, 127.1, 116.1, 60.1 ppm. HRMS (ESI ): calcd.
11.0 Hz, 1 H), 2.58 (q, J = 7.6 Hz, 2 H), 1.20 (t, J = 7.6 Hz, 3
for C33 29NNaO
H
2
SSi [M + Na]+ 554.1586; found 554.1584.
1
3
H) ppm. C NMR (CDCl
1
1
3
, 150 MHz): δ = 143.2, 139.8, 136.5,
(
E)-N-[2-Phenyl-2-(triphenylsilyl)vinyl]thiophene-2-sulfonamide (3r):
34.3, 133.4, 133.3, 133.2, 129.8, 129.4, 128.79, 128.72, 127.9,
26.9, 119.2, 28.6, 15.6 ppm. HRMS (ESI ): calcd. for
Eluent: hexane/ethyl acetate (10:1), yield 42 mg (80%). Off-white
solid; m.p. 156–157 °C. H NMR (CDCl , 600 MHz): δ = 7.68 (dd,
3
+
1
+
34 2
C H31NNaO SSi [M + Na] 568.1742; found 568.1743.
J = 6.2, J = 1.4 Hz, 1 H), 7.50 (dd, J = 4.1, J = 1.4 Hz, 1 H), 7.44–
(
(
E)-3-Methyl-N-[2-phenyl-2-(triphenylsilyl)vinyl]benzenesulfonamide
7.39 (m, 3 H), 7.37–7.27 (m, 12 H), 7.22–7.18 (m, 3 H), 7.18–7.15
3l): Eluent: hexane/ethyl acetate (10:1), yield 47 mg (89%). White
(m, 1 H), 6.74–6.69 (m, 2 H), 6.62 (d, J = 11.6 Hz, 1 H), 6.55 (d,
1
13
solid; m.p. 157–158 °C. H NMR (CDCl
3
, 600 MHz): δ = 7.54– J = 11.6 Hz, 1 H) ppm. C NMR (CDCl
3
, 150 MHz): δ = 140.5,
7
.50 (m, 2 H), 7.50–7.45 (m, 2 H), 7.44–7.39 (m, 3 H), 7.36–7.27
137.3, 136.5, 133.09, 133.07, 132.7, 132.6, 129.9, 129.3, 128.8,
+
(m, 12 H), 7.20–7.15 (m, 3 H), 6.71–6.66 (m, 2 H), 6.54 (d, J = 127.9, 127.7, 127.2, 120.1 ppm. HRMS (ESI ): calcd. for
1
3
2 2
S
Si [M + Na]+ 546.0994; found 546.0991.
1
1.6 Hz, 1 H), 6.51 (d, J = 11.6 Hz, 1 H), 2.47 (s, 3 H) ppm.
, 150 MHz): δ = 139.7, 139.6, 137.4, 136.4, 134.1,
33.6, 133.2, 130.0, 129.3, 128.8, 127.9, 127.17, 127.12, 124.0,
C
30
C H
25NNaO
NMR (CDCl
3
4
(
-Methyl-N-[2-phenyl-2-(triphenylsilyl)ethyl]benzenesulfonamide
1
1
1
4a): Yield 52 mg (97 %). Off-white solid; m.p. 166–167 °C. H
NMR (CDCl , 400 MHz): δ = 7.57 (d, J = 8.2 Hz, 2 H), 7.43–7.31
m, 3 H), 7.32–7.20 (m, 14 H), 7.26–7.03 (m, 3 H), 6.62 (d, J =
E)-4-Isopropyl-N-[2-phenyl-2-(triphenylsilyl)vinyl]benzenesulfon- 6.9 Hz, 2 H), 4.31 (dd, J = 6.4, J = 2.3 Hz, 1 H), 3.76–3.66 (m, 1
amide (3m): Eluent: hexane/ethyl acetate (10:1), yield 51 mg (91%). H), 3.39 (dt, J = 12.8, J = 2.8 Hz, 1 H), 3.06 (dd, J = 12.8, J =
+
2
19.0, 21.5 ppm. HRMS (ESI ): calcd. for C33H29NNaO SSi [M +
+
3
Na] 554.1586; found 554.1590.
(
(
1
13
White solid; m.p. 196–197 °C. H NMR (CDCl
3
, 600 MHz): δ = 3.7 Hz, 1 H), 2.42 (s, 3 H) ppm. C NMR (CDCl
3
, 100 MHz): δ
7
7
3
1
1
.63 (d, J = 8.2 Hz, 2 H), 7.44–7.39 (m, 5 H), 7.35–7.27 (m, 12 H), = 143.4, 138.1, 137.0, 136.3, 132.3, 130.0, 129.7, 129.4, 128.8, 128.0,
+
.20–7.15 (m, 3 H), 6.72–6.66 (m, 2 H), 6.57–6.51 (m, 2 H), 3.11–
.00 (m, 1 H), 1.34 (d, J = 6.9 Hz, 6 H) ppm. 13C NMR (CDCl
127.3, 126.4, 45.2, 35.8, 21.7 ppm. HRMS (ESI ): calcd. for
31NNaO
SSi [M + Na]+ 556.1742; found 556.1739.
3
,
C
33
H
2
50 MHz): δ = 154.9, 137.4, 137.1, 136.4, 133.7, 133.3, 129.9, 129.3,
4
-Methyl-N-[2-(p-tolyl)-2-(triphenylsilyl)ethyl]benzenesulfonamide
+
28.9, 127.9, 127.5, 127.1, 118.6, 34.4, 23.8 ppm. HRMS (ESI ):
1
(
4b): Yield 54 mg (98%). White solid; m.p. 198–199 °C. H NMR
CDCl , 400 MHz): δ = 7.57 (d, J = 6.9 Hz, 2 H), 7.42–7.34 (m, 3
+
calcd. for C35
H
33NNaO
2
SSi [M + Na] 582.1899; found 582.1904.
(
3
(
E)-4-Methoxy-N-[2-phenyl-2-(triphenylsilyl)vinyl]benzenesulfon- H), 7.32–7.18 (m, 14 H), 6.89 (d, J = 7.4 Hz, 2 H), 6.51 (d, J =
amide (3n): Eluent: hexane/ethyl acetate (7:1), yield 47 mg (86%). 6.4 Hz, 2 H), 4.29 (d, J = 8.7 Hz, 1 H), 3.73–3.63 (m, 1 H), 3.35
, 600 MHz): δ = (t, J = 12.8 Hz, 1 H), 3.00 (d, J = 11.5 Hz, 1 H), 2.43 (s, 3 H), 2.27
1
White solid; m.p. 177–178 °C. H NMR (CDCl
3
1
3
7
7
6
.63 (d, J = 8.9 Hz, 2 H), 7.43–7.38 (m, 3 H), 7.36–7.27 (m, 12 H), (s, 3 H) ppm. C NMR (CDCl
3
, 100 MHz): δ = 143.4, 137.0,
.20–7.16 (m, 3 H), 7.01 (d, J = 8.9 Hz, 2 H), 6.72–6.67 (m, 2 H), 136.3, 135.9, 134.7, 132.5, 130.0, 129.7, 129.5, 129.3, 128.0, 127.3,
+
.51 (d, J = 11.6 Hz, 1 H), 6.49 (d, J = 11.6 Hz, 1 H), 3.94 (s, 3
45.2, 35.1, 21. 7, 21.1 ppm. HRMS (ESI ) : cal cd. for
33NNaO
SSi, [M + Na]+ 570.1899; found 570.1896.
13
H) ppm. C NMR (CDCl
3
, 150 MHz): δ = 163.4, 137.5, 136.5,
C
34
H
2
1
1
33.8, 133.3, 131.4, 129.9, 129.3, 129.1, 128.9, 127.9, 127.1, 118.7,
N-[2-(3,5-Dimethylphenyl)-2-(triphenylsilyl)ethyl]-4-methylbenzene-
+
3
14.5, 55.9 ppm. HRMS (ESI ): calcd. for C33H29NNaO SSi [M +
sulfonamide (4c): Yield 53 mg (95%). Off-white solid; m.p. 154–
+
Na] 570.1535; found 570.1531.
1
1
55 °C. H NMR (CDCl
3
, 400 MHz): δ = 7.57 (d, J = 8.2 Hz, 2
(
(
E)-N-[2-Phenyl-2-(triphenylsilyl)vinyl]naphthalene-2-sulfonamide H), 7.43–7.34 (m, 3 H), 7.33–7.18 (m, 14 H), 6.74 (s, 1 H), 6.11 (s,
3o): Eluent: hexane/ethyl acetate (10:1), yield 51 mg (90%). White
2 H), 4.29 (d, J = 7.8 Hz, 1 H), 3.73–3.63 (m, 1 H), 3.30 (dt, J =
1
solid; m.p. 183–184 °C. H NMR (CDCl
1
7
(
1
1
3
, 600 MHz): δ = 8.29 (s, 12.8, J = 1.8 Hz, 1 H), 2.96 (dd, J = 12.8, J = 3.7 Hz, 1 H), 2.42
1
3
H), 7.08–7.97 (m, 3 H), 7.78–7.65 (m, 3 H), 7.41–7.35 (m, 3 H),
.28–7.19 (m, 12 H), 7.19–7.13 (m, 3 H), 6.70–6.63 (m, 3 H), 6.56
3
(s, 3 H), 2.05 (s, 6 H) ppm. C NMR (CDCl , 100 MHz): δ =
143.3, 137.9, 137.2, 136.8, 136.4, 136.3, 132.4, 129.9, 129.6, 128.0,
1
3
+
d, J = 12.4 Hz, 1 H) ppm. C NMR (CDCl
3
, 150 MHz): δ =
37.4, 136.5, 136.4, 135.1, 133.5, 133.1, 132.3, 129.8, 129.5, 129.3,
29.2, 128.8, 128.4, 128.2, 128.0, 127.9, 127.1, 121.9, 119.2 ppm.
127.9,127.3, 44.9, 35.0, 21.6, 21.2 ppm. HRMS (ESI ): calcd. for
35 2
C H35NNaO
SSi [M + Na]+ 584.2055; found 584.2051.
N-[2-(4-Ethylphenyl)-2-(triphenylsilyl)ethyl]-4-methylbenzenesulfon-
+
+
HRMS (ESI ): calcd. for C36
found 590.1588.
2
H29NNaO SSi [M + Na] 590.1586;
1
amide (4d): Yield 53 mg (94%). White solid; m.p. 181–182 °C. H
3
NMR (CDCl , 400 MHz): δ = 7.58 (d, J = 8.2 Hz, 2 H), 7.42–7.35
(
E)-N-[2-Phenyl-2-(triphenylsilyl)vinyl]methanesulfonamide (3p):
(m, 3 H), 7.32–7.18 (m, 14 H), 6.92 (d, J = 8.2 Hz, 2 H), 6.53 (d,
J = 8.2 Hz, 2 H), 4.28 (d, J = 7.8 Hz, 1 H), 3.74–3.64 (m, 1 H),
3.37 (dt, J = 12.8, J = 1.8 Hz, 1 H), 3.00 (dd, J = 12.8, J = 3.7 Hz,
Eluent: hexane/ethyl acetate (7:1), yield 34 mg (75%). White solid;
m.p. 167–168 °C. H NMR (CDCl , 600 MHz): δ = 7.46–7.38 (m,
3
1
Eur. J. Org. Chem. 2015, 4471–4480
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4477

H. Wang, H. Qiao, H. Zhang, H. Yang, Y. Zhao, H. Fu
1H NMR (CDCl
, 400 MHz): δ = 7.52 (d, J = 8.2 Hz, 2 H), 7.46–
7.36 (m, 3 H), 7.35–7.26 (m, 12 H), 7.21 (d, J = 7.8 Hz, 2 H), 7.16
(d, J = 8.2 Hz, 2 H), 6.48 (d, J = 8.2 Hz, 2 H), 4.40 (dd, J = 7.8,
FULL PAPER
1
3
1
3
H), 2.58 (q, J = 7.8 Hz, 2 H), 2.44 (s, 3 H), 1.21 (d, J = 7.8 Hz,
3
H) ppm. 13C NMR (CDCl
, 100 MHz): δ = 143.4, 142.5, 137.1,
3
36.3, 134.9, 132.6, 129.9, 129.7, 129.3, 128.3, 128.0, 127.4, 45.3,
5.2, 28. 5, 21. 7, 15.8 ppm. HRMS (ESI ): c alcd. for
+
J = 3.7 Hz, 1 H), 3.75–3.65 (m, 1 H), 3.32 (dt, J = 12.8, J = 3.6 Hz,
+
13
C
35
H
35NNaO
2
SSi [M + Na] 584.2055; found 584.2054.
1 H), 3.08 (dd, J = 12.8, J = 3.2 Hz, 1 H), 2.43 (s, 3 H) ppm.
NMR (CDCl
31.7, 131.0, 130.1, 129.7, 128.1, 127.2, 120.0, 45.1, 35.7, 21.7 ppm.
C
3
, 100 MHz): δ = 143.5, 137.6, 139.9, 136.2, 132.0,
N-[2-(4-Methoxyphenyl)-2-(triphenylsilyl)ethyl]-4-methylbenzene-
1
sulfonamide (4e): Yield 55 mg (97%). Off-white solid; m.p. 173–
+
+
1
HRMS (ESI ): calcd. for C33
34.0848; found 634.0852.
2
H30BrNNaO SSi [M + Na]
1
74 °C. H NMR (CDCl
3
, 400 MHz): δ = 7.57 (d, J = 8.3 Hz, 2
6
H), 7.42–7.35 (m, 3 H), 7.32–7.20 (m, 14 H), 6.63 (d, J = 8.7 Hz,
H), 6.53 (d, J = 8.7 Hz, 2 H), 4.32 (dd, J = 8.7, J = 2.3 Hz, 1
H), 3.74 (s, 3 H), 3.74–3.63 (m, 1 H), 3.32 (dt, J = 12.8, J = 2.3 Hz,
2
N-[2-Phenyl-2-(triphenylsilyl)ethyl]benzenesulfonamide (4k): Yield
1
48 mg (92 %). White solid; m.p. 162–163 °C. H NMR (CDCl ,
3
1
3
1
H), 3.00 (dd, J = 12.8, J = 3.7 Hz, 1 H), 2.42 (s, 3 H) ppm.
C
400 MHz): δ = 7.68 (d, J = 7.1 Hz, 2 H), 7.55 (t, J = 7.6 Hz, 1 H),
7.44 (t, J = 7.6 Hz, 2 H), 7.41–7.35 (m, 3 H), 7.33–7.19 (m, 12 H),
7.15–7.10 (m, 1 H), 7.06 (t, J = 7.6 Hz, 2 H), 6.61 (d, J = 7.4 Hz,
2 H), 4.34 (dd, J = 8.7, J = 2.3 Hz, 1 H), 3.79–3.69 (m, 1 H), 3.40
(dt, J = 12.8, J = 2.3 Hz, 1 H), 3.05 (dd, J = 12.8, J = 3.7 Hz, 1
3
NMR (CDCl , 100 MHz): δ = 158.2, 143.3, 137.0, 136.3, 132.5,
1
2
5
30.3, 130.0, 129.7, 129.6, 128.0, 127.3, 114.2, 55.3, 45.3, 34.5,
1.6 ppm. HRMS (ESI ): calcd. for C34
86.1848; found 586.1852.
+
H33NNaO
3
SSi [M + Na]+
1
3
H) ppm. C NMR (CDCl
3
, 100 MHz): δ = 140.0, 138.0, 136.3,
N-[2-(3-Methoxyphenyl)-2-(triphenylsilyl)ethyl]-4-methylbenzene-
sulfonamide (4f): Yield 52 mg (92%). Yellow solid; m.p. 161–162 °C.
1
32.7, 132.3, 130.0, 129.3, 129.1, 128.8, 128.0, 127.2, 126.4, 45.3,
+
+
1
32 29 2
35.8 ppm. HRMS (ESI ): calcd. for C H NNaO SSi [M + Na]
H NMR (CDCl
.37 (m, 3 H), 7.34–7.21 (m, 14 H), 7.03 (t, J = 7.8 Hz, 1 H), 6.68
dd, J = 8.2, J = 2.3 Hz, 1 H), 6.31 (d, J = 7.8 Hz, 1 H), 6.06 (s, 1
H), 4.28 (dd, J = 8.7, J = 2.3 Hz, 1 H), 3.75–3.65 (m, 1 H), 3.39 51 mg (96%). Off-white solid; m.p. 179–180 °C. H NMR (CDCl ,
3
, 400 MHz): δ = 7.56 (d, J = 8.2 Hz, 2 H), 7.44–
542.1586; found 542.1585.
7
(
N-[2-(p-Tolyl)-2-(triphenylsilyl)ethyl]benzenesulfonamide (4l): Yield
1
3
(
=
=
s, 3 H), 3.35 (dt, J = 12.8, J = 2.8 Hz, 1 H), 3.02 (dd, J = 12.8, J
400 MHz): δ = 7.68 (d, J = 7.8 Hz, 2 H), 7.55 (t, J = 7.4 Hz, 1 H),
, 100 MHz): δ 7.44 (t, J = 7.8 Hz, 2 H), 7.42–7.35 (m, 3 H), 7.34–7.18 (m, 12 H),
159.8, 143.4, 139.6, 136.9, 136.3, 132.4, 130.0, 129.7, 129.6, 128.0,
6.88 (d, J = 7.8 Hz, 2 H), 6.49 (d, J = 7.8 Hz, 2 H), 4.31 (d, J =
3.2 Hz, 1 H) 2.43 (s, 3 H) ppm. 13C NMR (CDCl
3
1
27.3, 122.1, 113.4, 113.2, 54.8, 45.3, 35.9, 21.7 ppm. HRMS 8.3 Hz, 1 H), 3.76–3.66 (m, 1 H), 3.36 (t, J = 12.4 Hz, 1 H), 3.00
+
+
13
(ESI ): calcd. for C34
H
33NNaO
3
SSi [M + Na] 586.1848; found
(dd, J = 12.8, J = 3.2 Hz, 1 H), 2.27 (s, 3 H) ppm. C NMR
586.1844.
(CDCl , 100 MHz): δ = 140.0, 136.3, 136.0, 134.6, 132.6, 132.5,
3
1
30.0, 129.5, 129.2, 129.1, 128.0, 127.2, 45.3, 35.1, 21.1 ppm.
N-[2-(2-Methoxyphenyl)-2-(triphenylsilyl)ethyl]-4-methylbenzene-
+
H31NNaO
2
SSi, [M + Na]+ 556.1742;
HRMS (ESI ): calcd. for C33
found 556.1740.
sulfonamide (4g): Yield 51 mg (91 %). Yellow solid; m.p. 165–
1
1
66 °C. H NMR (CDCl
3
, 400 MHz): δ = 7.54 (d, J = 8.4 Hz, 2
H), 7.40–7.31 (m, 3 H), 7.30–7.14 (m, 14 H), 7.08 (t, J = 7.8 Hz, 1
H), 6.64 (t, J = 7.8 Hz, 2 H), 6.43 (d, J = 7.4 Hz, 1 H), 4.26 (d, J
N-[2-(4-Ethylphenyl)-2-(triphenylsilyl)ethyl]benzenesulfonamide
1
(
4m): Yield 52 mg (95 %). Off-white solid; m.p. 165–166 °C. H
NMR (CDCl , 400 MHz): δ = 7.69 (d, J = 7.8 Hz, 2 H), 7.56 (t, J
7.3 Hz, 1 H), 7.45 (t, J = 7.8 Hz, 2 H), 7.42–7.35 (m, 3 H), 7.33–
.18 (m, 12 H), 6.91 (d, J = 8.2 Hz, 2 H), 6.52 (d, J = 7.8 Hz, 2
H), 4.32 (d, J = 7.8 Hz, 1 H), 3.76–3.66 (m, 1 H), 3.38 (dt, J =
2.8, 2.3 Hz, 1 H), 2.99 (dd, J = 12.8, J = 3.7 Hz, 1 H), 2.58 (q, J
=
7.4 Hz, 1 H), 3.70–3.58 (m, 2 H), 3.42 (t, J = 12.8 Hz, 1 H), 3.26
3
13
(
1
1
s, 3 H), 2.42 (s, 3 H) ppm. C NMR (CDCl
3
, 100 MHz): δ =
57.5, 143.1, 136.8, 136.1, 133.0, 129.7, 129.6, 128.5, 127.8, 127.3,
27.2, 126.4, 120.7, 110.7, 54.7, 44.4, 27.3, 21.7 ppm. HRMS
=
7
+
+
(ESI ): calcd. for C34
3
H33NNaO SSi [M + Na] 586.1848; found
1
=
586.1851.
13
3
7.8 Hz, 2 H), 1.21 (t, J = 7.8 Hz, 3 H) ppm. C NMR (CDCl ,
N-[2-(4-Fluorophenyl)-2-(triphenylsilyl)ethyl]-4-methylbenzene-
sulfonamide (4h): Yield 53 mg (96%). White solid; m.p. 169–170 °C.
100 MHz): δ = 142.5, 140.0, 136.3, 134.9, 132.7, 132.5, 130.0, 129.3,
129.1, 128.3, 128.0, 127.3, 45.3, 35.2, 28.5, 15.7 ppm. HRMS
1
+
H33NNaO
2
SSi [M + Na]+ 570.1899; found
H NMR (CDCl
.34 (m, 3 H), 7.33–7.15 (m, 14 H), 6.79–6.69 (m, 2 H), 6.62–6.52
m, 2 H), 4.40 (d, J = 7.3 Hz, 1 H), 3.74–3.64 (m, 1 H), 3.33 (t, J
3
, 400 MHz): δ = 7.54 (d, J = 6.9 Hz, 2 H), 7.44–
(ESI ): calcd. for C34
570.1895.
7
(
=
N-[2-(4-Methoxyphenyl)-2-(triphenylsilyl)ethyl]benzenesulfonamide
1
3
12.8 Hz, 1 H), 3.08 (d, J = 12.8 Hz, 1 H), 2.42 (s, 3 H) ppm.
, 100 MHz): δ = 161.5 (d, J = 243.1 Hz), 143.4, 136.9,
36.2, 133.9, 132.2, 130.7 (d, J = 7.6 Hz), 130.1, 129.7, 128.1, 127.2,
C
1
(
(
7
7
4n): Yield 53 mg (97%). White solid; m.p. 154–155 °C. H NMR
CDCl , 400 MHz): δ = 7.68 (d, J = 7.4 Hz, 2 H), 7.55 (t, J =
.3 Hz, 1 H), 7.44 (t, J = 7.8 Hz, 2 H), 7.42–7.35 (m, 3 H), 7.33–
.18 (m, 12 H), 6.63 (d, J = 8.7 Hz, 2 H), 6.52 (d, J = 8.7 Hz, 2
NMR (CDCl
1
1
3
3
+
15.5 (d, J = 21.0 Hz), 45.3, 35.2, 21.6 ppm. HRMS (ESI ): calcd.
+
for C33
2
H30FNNaO SSi [M + Na] 574.1648; found 574.1640.
H), 4.32 (d, J = 8.7 Hz, 1 H), 3.76–3.66 (m, 1 H), 3.75 (s, 3 H),
3.33 (dt, J = 12.8, 2.3 Hz, 1 H), 2.99 (dd, J = 12.8, J = 3.7 Hz, 1
N-[2-(4-Chlorophenyl)-2-(triphenylsilyl)ethyl]-4-methylbenzene-
1
3
sulfonamide (4i): Yield 52 mg (92 %). Off-white solid; m.p. 189– H) ppm. C NMR (CDCl
3
, 100 MHz): δ = 158.2, 140.0, 136.3,
1
1
90 °C. H NMR (CDCl
3
, 400 MHz): δ = 7.53 (d, J = 7.8 Hz, 2
132.7, 132.5, 130.3, 130.0, 129.6, 129.1, 128.0, 127.2, 114.3, 55.4,
+
H), 7.44–7.35 (m, 3 H), 7.34–7.22 (m, 12 H), 7.21 (d, J = 7.8 Hz, 45.4, 34.6 ppm. HRMS (ESI ): calcd. for C33
H
3
31NNaO SSi [M +
+
2
H), 7.01 (d, J = 8.2 Hz, 2 H), 6.54 (d, J = 8.2 Hz, 2 H), 4.44 (dd, Na] 572.1692; found 572.1688.
J = 7.3, J = 3.9 Hz, 1 H), 3.74–3.64 (m, 1 H), 3.33 (dt, J = 12.8, J
3.7 Hz, 1 H), 3.09 (dd, J = 12.8, J = 2.8 Hz, 1 H), 2.42 (s, 3
N-[2-(4-Chlorophenyl)-2-(triphenylsilyl)ethyl]benzenesulfonamide
=
1
(
4o): Yield 51 mg (92 %). Off-white solid; m.p. 172–173 °C. H
NMR (CDCl , 400 MHz): δ = 7.66 (d, J = 7.8 Hz, 2 H), 7.56 (t, J
7.3 Hz, 1 H), 7.51–7.37 (m, 5 H), 7.36–7.16 (m, 12 H), 7.03 (d,
13
H) ppm. C NMR (CDCl
3
, 100 MHz): δ = 143.5, 137.0, 136.9,
3
1
3
+
36.2, 132.1, 132.0, 130.6, 130.1, 129.7, 128.7, 128.1, 127.2, 45.2,
=
+
2
5.6, 21.7 ppm. HRMS (ESI ): calcd. for C33H30ClNNaO SSi [M
J = 7.4 Hz, 2 H), 6.53 (d, J = 7.8 Hz, 2 H), 4.37 (d, J = 8.4 Hz, 1
H), 3.78–3.66 (m, 1 H), 3.34 (dt, J = 12.8, 2.3 Hz, 1 H), 3.08 (dd,
+
Na] 590.1353; found 590.1347.
N-[2-(4-Bromophenyl)-2-(triphenylsilyl)ethyl]-4-methylbenzene-
sulfonamide (4j): Yield 57 mg (93%). White solid; m.p. 192–193 °C. = 139.9, 136.9, 136.2, 132.7, 132.1, 132.0, 130.6, 130.2, 129.1, 128.8,
1
3
3
J = 12.4, J = 2.3 Hz, 1 H) ppm. C NMR (CDCl , 100 MHz): δ
4478
www.eurjoc.org
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 4471–4480

Rhodium-Catalyzed Hydrosilylation of N-Sulfonyl-1,2,3-triazoles
+
1
C
28.1, 127.2, 45.2, 35.6 ppm. HRMS (ESI ): calcd. for
6-Methyl-1-tosyl-3-(triphenylsilyl)-1H-indole (5b): Eluent: hexane/
+
32
H
28ClNNaO
2
SSi [M + Na] 576.1196; found 576.1194.
ethyl acetate (15:1), yield 41 mg (75%). Yellow solid; m.p. 144–
1
1
45 °C. H NMR (CDCl
3
, 600 MHz): δ = 7.80 (s, 1 H), 7.75 (d, J
4
(
(
-Methoxy-N-[2-phenyl-2-(triphenylsilyl)ethyl]benzenesulfonamide
4p): Yield 51 mg (93%). Yellow solid; m.p. 175–176 °C. H NMR
CDCl , 400 MHz): δ = 7.61 (d, J = 7.8 Hz, 2 H), 7.44–7.35 (m, 3
H), 7.34–7.18 (m, 12 H), 7.16–7.04 (m, 3 H), 6.90 (d, J = 7.3 Hz,
H), 6.63 (d, J = 7.8 Hz, 2 H), 4.28 (d, J = 8.2 Hz, 1 H), 3.86 (s,
H), 3.74–3.64 (m, 1 H), 3.39 (t, J = 12.8 Hz, 1 H), 3.07 (dd, J =
, 100 MHz): δ =
62.9, 138.1, 136.3, 132.4, 131.5, 130.0, 129.4, 129.3, 128.8, 128.0,
=
8.3 Hz, 2 H), 7.60–7.53 (m, 6 H), 7.47–7.41 (m, 4 H), 7.40–7.33
1
(
(
(
1
2
m, 6 H), 7.25 (d, J = 6.9 Hz, 2 H), 7.06 (d, J = 7.6 Hz, 1 H), 6.89
3
1
3
d, J = 8.2 Hz, 1 H), 2.45 (s, 3 H), 2.38 (s, 3 H) ppm. C NMR
CDCl , 150 MHz): δ = 145.1, 136.7, 136.2, 135.47, 135.42, 134.8,
33.9, 132.6, 130.1, 130.0, 128.2, 127.0, 124.9, 123.1, 113.7, 113.2,
3
2
3
1
1
1
+
2
2.0, 21.8 ppm. HRMS (ESI ): calcd. for C34H29NNaO SSi [M +
2.8, J = 2.7 Hz, 1 H) ppm. 13C NMR (CDCl
3
+
Na] 566.1586; found 566.1581.
+
General Procedure for Synthesis of Compounds 6:[15] To a stirred
solution of compound 4 (0.1 mmol) in THF (1.0 mL) was added a
26.4, 114.2, 55.7, 45.2, 35.8 ppm. HRMS (ESI ): calcd. for
+
C
33
H
31NNaO
3
SSi [M + Na] 572.1692; found 572.1693.
solution of NaOH (0.2 mmol, 8 mg) in H
2
O (0.1 mL), followed by
4
-Bromo-N-[2-phenyl-2-(triphenylsilyl)ethyl]benzenesulfonamide
TBAF·3H O (0.12 mmol, 38 mg). The mixture was stirred at 60 °C
2
1
(
4q): Yield 57 mg (95 %). Off-white solid; m.p. 185–186 °C. H
NMR (CDCl , 400 MHz): δ = 7.55 (d, J = 8.8 Hz, 2 H), 7.49 (d,
J = 8.4 Hz, 2 H), 7.45–7.36 (m, 3 H), 7.34–7.19 (m, 12 H), 7.16–
.11 (m, 1 H), 7.11–7.04 (m, 2 H), 6.63 (d, J = 8.0 Hz, 2 H), 4.41
d, J = 7.8 Hz, 1 H), 3.74–3.64 (m, 1 H), 3.39 (t, J = 12.8 Hz, 1
for 2 h (TLC). The resulting solution was extracted with ethyl acet-
ate (3ϫ 1.0 mL), and the combined organic layer was washed with
brine, dried with anhydrous Na SO , filtered, and concentrated.
2 4
The residue was purified by column chromatography on silica gel
with hexane/ethyl acetate as the eluent to give desired target prod-
uct 6.
3
7
(
13
H), 3.07 (d, J = 12.4 Hz, 1 H) ppm. C NMR (CDCl
δ = 138.9, 138.0, 136.3, 132.3, 132.2, 130.1, 129.3, 128.8, 128.7,
1
C
3
, 100 MHz):
+
28.1, 127.6, 126.5, 45.4, 36.0 ppm. HRMS (ESI ): calcd. for
4-Methyl-N-phenethylbenzenesulfonamide (6a): Eluent: hexane/ethyl
acetate (10:1), yield 24 mg (87%). Yellow solid; m.p. 49–50 °C
+
32
H
28BrNNaO
2
SSi [M + Na] 620.0691; found 620.0688.
16]
1
(
ref.[ 51–53 °C). H NMR (CDCl
3
, 600 MHz): δ = 7.69 (d, J =
.3 Hz, 2 H), 7.31–7.24 (m, 4 H), 7.24–7.19 (m, 1 H), 7.08 (d, J =
.9 Hz, 2 H), 4.45 (t, J = 5.5 Hz, 1 H), 3.21 (q, J = 6.8 Hz, 2 H),
N-[2-Phenyl-2-(triphenylsilyl)ethyl]-4-(trifluoromethyl)benzenesulf-
8
6
2
1
1
onamide (4r): Yield 57 mg (97%). Off-white solid; m.p. 138–139 °C.
1
3
H NMR (CDCl , 400 MHz): δ = 7.74 (d, J = 6.9 Hz, 2 H), 7.66
1
3
3
.75 (t, J = 6.8 Hz, 2 H), 2.42 (s, 3 H) ppm. C NMR (CDCl ,
50 MHz): δ = 143.6, 137.8, 136.9, 129.8, 128.88, 128.85, 127.2,
26.9, 44.3, 35.9, 21.7 ppm. MS (ESI): m/z = 298.2 [M + Na] .
(
7
(
d, J = 6.9 Hz, 2 H), 7.45–7.36 (m, 3 H), 7.34–7.19 (m, 12 H), 7.15–
.09 (m, 1 H), 7.08–7.01 (m, 2 H), 6.61 (d, J = 6.9 Hz, 2 H), 4.51
d, J = 7.8 Hz, 1 H), 3.78–3.68 (m, 1 H), 3.40 (t, J = 12.8 Hz, 1
+
13
H), 3.08 (d, J = 12.8 Hz, 1 H) ppm. C NMR (CDCl
δ = 143.5, 137.9, 136.3, 134.2 (q, J = 33.4 Hz), 132.2, 130.1, 129.3,
3
, 100 MHz): 4-Methyl-N-(4-methylphenethyl)benzenesulfonamide (6b): Eluent:
hexane/ethyl acetate (15:1), yield 24 mg (83%). Off-white solid;
1
128.8, 128.1, 127.6, 126.5, 126.2, 123.4 (q, J = 271.7 Hz), 45.5,
3
m.p. 84–85 °C. H NMR (CDCl , 600 MHz): δ = 7.69 (d, J =
+
3
6.1 ppm. HRMS (ESI ): calcd. for C33
H
28
F
3
NNaO
2
SSi [M + Na] 8.2 Hz, 2 H), 7.28 (d, J = 7.6 Hz, 2 H), 7.07 (d, J = 7.6 Hz, 2 H),
6.96 (d, J = 7.6 Hz, 2 H), 4.48 (t, J = 6.2 Hz, 1 H), 3.18 (q, J =
+
610.1460; found 610.1456.
6
.9 Hz, 2 H), 2.71 (t, J = 6.9 Hz, 2 H), 2.43 (s, 3 H), 2.31 (s, 3
N-[2-Phenyl-2-(triphenylsilyl)ethyl]methanesulfonamide (4s): Yield
1
3
H) ppm. C NMR (CDCl
1
3
, 150 MHz): δ = 143.5, 137.0, 136.5,
1
41 mg (90%). Off-white solid; m.p. 185–186 °C. H NMR (CDCl
3
,
29.8, 129.5, 128.7, 127.2, 44.4, 35.4, 21.6, 21.1 ppm. HRMS
600 MHz): δ = 7.47–7.42 (m, 3 H), 7.40–7.28 (m, 12 H), 7.21–7.14
+
H19NNaO
2
S [M + Na]+ 312.1034; found
(
3
ESI ): calcd. for C16
12.1028.
(m, 3 H), 6.89–6.83 (m, 2 H), 4.16 (dd, J = 8.2, J = 3.4 Hz, 1 H),
3
.93–3.85 (m, 1 H), 3.59 (dt, J = 13.0, J = 4.1 Hz, 1 H), 3.24 (dd,
13
J = 12.4, J = 3.4 Hz, 1 H), 2.69 (s, 3 H) ppm. C NMR (CDCl
3
,
Supporting Information (see footnote on the first page of this arti-
cle): Copies of H and C NMR spectra of compounds IIba, 3, 4,
5.9, 40.5, 36.9 ppm. HRMS (ESI ): calcd. for C27H27NNaO
2
SSi 5, and 6.
1
13
1
4
[
50 MHz): δ = 138.6, 136.3, 132.5, 130.1, 129.6, 128.9, 128.1, 126.6,
+
M + Na]+ 480.1429; found 480.1420.
General Procedure for Synthesis of Compounds 5:[14] An oven-dried
5 mL Schlenk tube was cooled under vacuum. Compound 3
0.1 mmol), Pd(OAc) (0.01 mmol, 2.2 mg), and Cu(OAc)
0.1 mmol, 18 mg) were added to the tube. The tube was evacuated
three times. The reaction was stirred at 120 °C
balloon for 12 h (TLC). The reaction mixture was con-
Acknowledgments
2
(
(
2
2
The authors wish to thank the National Natural Science Founda-
tion of China (NSFC) (grant numbers 21172128, 21372139, and
and refilled with O
under O
2
21221062), and the Ministry of Science and Technology of China
2
(
grant number 2012CB722605) for financial support.
centrated under reduced pressure, and the residue was purified by
column chromatography on silica gel with hexane/ethyl acetate as
the eluent to give desired target product 5.
[
1] K. C. Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem. Int. Ed.
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-Tosyl-3-(triphenylsilyl)-1H-indole (5a): Eluent: hexane/ethyl acet-
[2] K. Oshima, in: Science of Synthesis (Ed.: I. Fleming), Thieme,
Stuttgart, Germany, 2002, vol. 4, p. 713–756.
1
ate (15:1), yield 38 mg (72%). Off-white solid; m.p. 135–136 °C. H
NMR (CDCl , 600 MHz): δ = 7.97 (d, J = 8.2 Hz, 1 H), 7.75 (d,
J = 8.3 Hz, 2 H), 7.62–7.56 (m, 6 H), 7.49 (s, 1 H), 7.47–7.41 (m,
[
3] a) I. Ojima, Z. Li, J. Zhu, in: The Chemistry of Organosilicon
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Shafir, R. Pleixats, T. Parella, Adv. Synth. Catal. 2014, 356,
3
3
8
2
1
1
H), 7.40–7.33 (m, 6 H), 7.28 (t, J = 6.9 Hz, 1 H), 7.25 (d, J =
.3 Hz, 2 H), 7.18 (d, J = 8.3 Hz, 1 H), 7.06 (t, J = 6.9 Hz, 1 H),
.37 (s, 3 H) ppm. 13C NMR (CDCl
, 100 MHz): δ = 145.2, 136.2,
3
36.1, 135.9, 135.3, 134.9, 133.8, 130.1, 130.0, 128.2, 127.1, 124.6,
+
23.5, 123.4, 113.6, 113.3, 21.8 ppm. HRMS (ESI ): calcd. for
+
C
33
H
27NNaO
2
SSi [M + Na] 552.1429; found 552.1426.
Eur. J. Org. Chem. 2015, 4471–4480
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4479

H. Wang, H. Qiao, H. Zhang, H. Yang, Y. Zhao, H. Fu
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Received: April 9, 2015
Published Online: June 2, 2015
4480
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Eur. J. Org. Chem. 2015, 4471–4480