Polystyrene-supported TBD catalyzed ring-opening of N-tosylaziridines with silylated nucleophiles

Article abstract of DOI:10.1039/c2ob25435b

Polystyrene-supported TBD (PS-TBD) catalyzes the ring-opening of N-tosylaziridines with silylated nucleophiles to give the corresponding products in high yields. PS-TBD was easily recovered and reused without significant loss of catalytic activity.

Full text of DOI:10.1039/c2ob25435b

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PAPER
Polystyrene-supported TBD catalyzed ring-opening of N-tosylaziridines with
silylated nucleophiles†‡
Satoru Matsukawa,* Takeru Harada and Shiori Yasuda
Received 28th February 2012, Accepted 1st May 2012
DOI: 10.1039/c2ob25435b
Polystyrene-supported TBD (PS-TBD) catalyzes the ring-opening of N-tosylaziridines with silylated
nucleophiles to give the corresponding products in high yields. PS-TBD was easily recovered and reused
without significant loss of catalytic activity.
openings of epoxides, aldol-type condensations and Michael
Introduction
additions.11 We have also reported cyanosilylation of aldehydes,
ketones and imines catalyzed by PS-TBD.12 In an effort to apply
Aziridines are very useful intermediates for the synthesis of
numerous nitrogen-containing biologically active compounds.1
PS-TBD to other useful reactions, ring-opening of aziridines
Therefore, nucleophilic ring-opening of aziridines by various
approaches has been widely examined and developed.2 Among
these approaches, the ring-opening reaction using silylated
nucleophiles, such as silyl cyanide, azide or halides, is important
to produce highly functionalized compounds. Therefore, the cat-
alytic ring-opening reaction with silylated nucleophiles using
Lewis acids3 and fluoride ions4 has been developed to realize
high yields and selectivities. Recently, Lewis base-catalyzed
reactions have also been reported.5 In search of a broadly appli-
cable and environmentally friendly reaction, we used a polymer-
supported organobase, 1,5,7-triazabicyclo[4,4,0]dec-5-ene poly-
styrene (PS-TBD) as a Lewis base catalyst.
with various silylated nucleophiles were examined.
Results and discussion
Initially, the ring-opening reaction of N-tosylaziridine 1a with
trimethylsilyl cyanide was examined in the presence of 5 mol%
of PS-TBD in DMF at room temperature. However, the reaction
was very slow. Then the reaction was performed at elevated
temperature. The desired product was obtained at 95% yield in
4 h at 80 °C. The product was obtained in low yield when other
polymer-supported bases, such as PS-DIEA, PS-TPP, and
Polymer-supported catalysts have attracted much attention in
recent decades due to their inherent advantages in synthetic
chemistry, e.g., simplification of reaction procedures including
easy recovery of the catalyst by filtration, application to auto-
mated systems, and recycling of catalyst.6 PS-TBD is a polymer-
supported organocatalyst, which consists of a highly basic guani-
dine moiety, TBD7 anchored on polystyrene. It has been used to
mediate the alkylation of phenols, amines, active methylene
compounds and thiols, the esterification of carboxylic acids, the
dehalogenation of organic halides and the high throughput syn-
thesis of aryl triflates and aryl nonaflates.8 PS-TBD also acts as a
good catalyst for the Henry reaction and the addition of dialkyl
phosphites to a variety of carbonyl compounds and imines.9,10
Recently, Fringuelli et al. reported PS-TBD catalyzed ring-
Table 1 Optimization of the reaction conditions
Entry
Base
Solvent
Yield (%)
1
2
3
4
5
6
DMF
95
11
Trace
10
Trace
48
DMFa
THFb
MeCNc
Toluene
SFCd
7
8
9
PS-DIEAe
PS-TPPf
DMF
DMF
DMF
15
Trace
8
Department of Science Education, Faculty of Education, Ibaraki
University, Ibaraki, 310-8512 Japan.
E-mail: smatsuka@mx.ibaraki.ac.jp; Fax: +81 29 228 8234
†Electronic supplementary information (ESI) available: Copies of 1H
and 13C NMR Spectra of products 2a–2g, 3a–3g, 3a′, 3a′′, 3c′′, 3e′,
3e′′ and 3g′. See DOI: 10.1039/c2ob25435b
PS-DMAPg
a At room temperature. b At 66 °C (reflux condition). c At 82 °C (reflux
condition). d SFC: solvent free condition. e PS-DIEA: N,N-(Diisopropyl)
aminomethyl polystyrene. f PS-TPP: Diphenylphosphinopolystyrene.
g PS-DMAP: N-(Methyl polystyrene)-4-(methylamino)pyridine.
‡This article is part of the joint ChemComm–Organic & Biomolecular
Chemistry ‘Organocatalysis’ web themed issue.
4886 | Org. Biomol. Chem., 2012, 10, 4886–4890
This journal is © The Royal Society of Chemistry 2012

PS-DMAP were used (Table 1, entries 1 vs. 7–9). The reactions
performed in THF, MeCN and toluene were inferior when com-
pared with that performed in DMF. We also examined the reac-
tion in SFC (solvent free condition), however, the yield was not
satisfactory (Table 1, entry 6).
In order to clarify the scope of this reaction, several N-tosyl-
aziridines were examined in the presence of 5 mol% PS-TBD
(Table 2). High yields of the corresponding products were
obtained for both 2-substituted aziridines and 2,3-disubstituted
aziridines. In the case of 2-substituted aziridines, the reaction
proceeded smoothly when 1 mol% of PS-TBD was used.
Almost complete regioselectivity (>98 : 2) was observed when
using both phenyl- and alkyl-substituted aziridines. Unfortu-
nately, in the case of less reactive aziridine, 2,3-diphenylaziridine
1g, the yield was unsatisfactory.
using both 2-substituted aziridines and 2,3-disubstituted aziri-
dines. 2,3-Diphenylaziridine also gave good results. High level
of regioselectivity (>95 : 5) was observed when using alkyl-sub-
stituted aziridines as substrates. On the other hand, for phenyl-
substituted aziridine 1f with TMSN3, the regioselectivity was not
satisfactory. Although the reason is not clear, we consider the
electronic effects as one possibility.
Table 3 PS-TBD catalyzed ring-opening of aziridines with other
silylated nucleophiles
The TBD-catalyzed reaction was also applicable to other sily-
lated nucleophiles, trimethylsilyl azide and halides (Table 3).
The reaction proceeded smoothly at room temperature in high
yields. High yields of the corresponding product were obtained
Entry
1
Aziridine
Nu
N3
Product
Time
8 h
Yielda,b (%)
1a
94 (3a)
Table 2 PS-TBD catalyzed ring-opening of various aziridines with
Me3SiCN
2
3
4
Cl
Br
N3
2 h
97 (3a′)
97 (3a′′)
88 (3b)
2 h
1b
1c
12 h
Entry
1
Aziridine
Product
Time
4 h
Yielda (%)
95
5
6
7
N3
Cl
8 h
2 h
8 h
95 (3c)
90 (3c′)
82 (3d)
2
12 h
89
1d
1e
N3
3
4 h
12 h
91
85
8
N3
Cl
Br
N3
8 h
1 h
1 h
12 h
92 (3e)
98 (3e′)
4b
9
5
4 h
95
10
11
98 (3e′′)
1f
97 (3f, 4f)c
6
4 h
95
94
12
12d
13d
1g
N3
Cl
8 h
80 (3g)
75 (3g′)
7
4 h
8c
12 h
1g
12 h
a Isolated yield. b The product was obtained as 3a–g unless otherwise
noted. c Regioisomer ratio 3f : 4f = 22 : 78. d The reaction was carried
out at 30 °C.
a Isolated yield. b 1 mol% of PS-TBD was used. c The reaction was
carried out at 100 °C.
This journal is © The Royal Society of Chemistry 2012
Org. Biomol. Chem., 2012, 10, 4886–4890 | 4887

General procedure for PS-TBD catalyzed ring-opening of
aziridines with silylated nucleophiles
To a solution of PS-TBD (0.05 mmol) in DMF (1 mL) was
added aziridine (1.0 mmol) and silylated nucleophile
(1.25 mmol) at room temperature or 80 °C. After the reaction
was complete (as determined by TLC), EtOAc (5 ml) was added
to the mixture and PS-TBD was separated by filtration. The
filtrate was concentrated under vacuum and purified by column
chromatography on silica gel (EtOAc–hexane = 1 : 3) to give the
corresponding product. The recovered catalyst is reusable after
washing (acetone and water) and drying in vacuo.
N-(2-Cyanocyclohexyl)-4-methylbenzenesulfonamide.4
(2a).
IR (KBr, cm−1) 3250, 2250, 1620; H NMR (500 Hz, CDCl3) δ
1.20–1.38 (m, 3H), 1.51–1.67 (m, 3H), 1.86–1.94 (m, 1H),
1.97–2.04 (m, 1H), 2.43 (s, 3H), 2.66 (brs, 1H), 3.35 (dq, J =
4.6, 8.0 Hz, 1H), 5.32 (d, J = 8.0 Hz, 1H), 7.32 (d, J = 8.5 Hz,
2H), 7.80 (d, J = 8.5 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ
21.5, 22.6, 229, 27.1, 31.4, 34.4, 52.7, 120.2, 127.2, 129.8,
137.1, 143.9; HRMS (FAB): for C14H19N2O2S (M + H)+ calcd
279.1167, found 279.1169.
1
N-(2-Cyanocyclopentyl)-4-methylbenzenesulfonamide.4 (2b).
1
IR (KBr, cm−1) 3260, 2250, 1600; H NMR (500 Hz, CDCl3) δ
1.40–1.48 (m, 1H), 1.64–1.73 (m, 2H), 1.74–1.85 (m, 1H),
1.86–1.96 (m, 1H), 2.00–2.07 (m, 1H), 2.41 (s, 3H), 2.83 (dt, J
= 6.0, 8.5 Hz, 1H), 3.69–3.75 (m, 1H), 5.71 (d, J = 7.0 Hz, 1H),
7.30 (d, J = 8.0 Hz, 2H), 7.77 (d, J = 8.0 Hz, 2H); 13C NMR
(125 MHz, CDCl3) δ 21.4, 22.6, 28.9, 32.5, 35.6, 58.6, 121.1,
127.2, 129.9, 136.5, 144.0; HRMS (FAB): for C13H17N2O2S (M
+ H)+ calcd 265.1011, found 265.1021.
Scheme 1 Reuse of recovered PS-TBD.
The recovery and reuse of PS-TBD are illustrated for the reac-
tion of N-tosylaziridine 1a with trimethylsilyl cyanide in
Scheme 1. After the reaction was completed, ethyl acetate was
added to the reaction mixture and the catalyst was recovered by
filtration. The recovered catalyst was washed, dried and then
reused. The catalyst maintained its catalytic activity after four
runs. The same result was observed in the reaction with tri-
methylsilyl azide.
N-(2-Cyanooctyl)-4-methylbenzenesulfonamide.4
(2c). IR
(neat, cm−1) 3310, 2250, 1600; H NMR (500 Hz, CDCl3) δ
0.81 (t, J = 7.5 Hz, 3H), 1.07–1.20 (m, 8H), 1.47–1.58 (m, 2H),
2.41 (s, 3H), 2.54 (dd, J = 3.5, 16.5 Hz, 1H), 2.64 (dd, J = 6.0,
16.5 Hz, 1H), 3.38–3.41 (m, 1H), 4.83 (d, J = 8.0 Hz, 1H), 7.31
(d, J = 8.0 Hz, 2H), 7.75 (d, J = 8.0 Hz, 2H); 13C NMR
(125 MHz, CDCl3) δ 14.0, 21.5, 22.4, 25.0, 25.2, 28.4, 31.4,
33.9, 50.0, 116.7, 127.0, 129.9, 137.0, 144.0; HRMS (FAB): for
C16H25N2O2S (M + H)+ calcd 308.1558, found 308.1552.
1
Conclusions
In conclusion, we demonstrated that PS-TBD catalyze ring-
opening reactions of aziridines with silylated nucleophiles. A
broad range of silyl nucleophiles, including silyl cyanide, azide
and halides, could be applied under mild conditions using 5 mol
% PS-TBD. Furthermore, PS-TBD was easily recovered and
reused without loss of activity after 4 runs. These reactions
provide a simple and environmentally friendly route to the syn-
thesis of precursor materials to highly functionalized β-amino
acids, 1,2-diamines and 1,3-diamines.
N-(2-Cyanohexyl)-4-methylbenzenesulfonamide.4
(2d). IR
(neat, cm−1) 3270, 2240, 1600; H NMR (500 Hz, CDCl3) δ
0.82 (t, J = 7.5 Hz, 3H), 1.08–1.24 (m, 4H), 1.47–1.58 (m, 2H),
2.41 (s, 3H), 2.55 (dd, J = 4.0, 16.5 Hz, 1H), 2.65 (dd, J = 6.0,
16.5 Hz, 1H), 3.38–3.42 (m, 1H), 4.80–4.83 (m, 1H), 7.31 (d,
J = 8.0 Hz, 2H), 7.75 (d, J = 8.0 Hz, 2H); 13C NMR (125 MHz,
CDCl3) δ 14.1, 21.7, 25.1, 28.8, 31.4, 33.4, 50.5, 116.6, 127.2,
129.8, 137.5, 143.9; Anal. Found: C, 60.12; H 7.28; N 9.79.
Calcd for C14H20N2O2S: C, 59.97; H 7.19; N 9.99%.
1
Experimental
All reactions were performed under an argon atmosphere using
oven-dried glassware. Flash column chromatography was per-
formed using silica gel Wakogel C-200. Preparative thin-layer
chromatography was carried out on silica gel Wakogel B-5F.
Dehydrate DMF, THF, toluene and CH3CN were purchased from
Wako Chemical. Other commercially available reagents was
used as received without further purification. The aziridines were
prepared according to literature procedure.13
N-(2-Cyano-1-benzylethyl)-4-methylbenzenesulfonamide.5a
(2e). IR (KBr, cm−1) 3270, 2250, 1600; 1H NMR (500 Hz,
CDCl3) δ 2.42 (s, 3H), 2.54 (dd, J = 4.0, 14.0 Hz, 1H), 2.64 (dd,
J = 6.0, 14.0 Hz, 1H), 2.74 (dd, J = 8.0, 4.0 Hz, 1H), 2.88 (dd,
J = 7.5, 14.0 Hz, 1H), 3.57–3.64 (m, 1H), 4.82–4.88 (m, 1H),
6.97 (d, J = 7.6 Hz, 2H), 7.18–7.20 (m, 5H), 7.53 (d, J = 8.0
Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 21.5, 24.1, 39.7, 51.3,
116.7, 126.9, 127.3, 128.9, 129.0, 129.8, 135.0, 136.3, 143.8.;
4888 | Org. Biomol. Chem., 2012, 10, 4886–4890
This journal is © The Royal Society of Chemistry 2012

HRMS (FAB): for C17H19N2O2S (M + H)+ calcd 315.1167,
found 315.1166.
CDCl3) δ 0.82 (t, J = 7.0 Hz, 3H), 1.10–1.50 (m, 10H), 2.41 (s,
3H), 3.26–3.30 (m, 3H), 4.80 (d, J = 7.0 Hz, 1H), 7.28 (d, J =
8.0 Hz, 2H), 7.74 (d, J = 8.0 Hz, 2H); 13C NMR (125 MHz,
CDCl3) δ 14.0, 21.5, 22.4, 25.3, 28.8, 31.6, 32.6, 53.2, 55.0,
127.0, 129.7, 137.7, 143.6; HRMS (FAB): for C15H25N4O2S
(M + H)+ calcd 325.1698, found 325.1698.
N-(2-Cyano-1-phenylethyl)-4-methylbenzenesulfonamide.4
(2f). IR (KBr, cm−1) 3280, 2250, 1590; 1H NMR (500 Hz,
CDCl3) δ 2.39 (s, 3H), 2.87 (dd, J = 7.0, 17.0 Hz, 1H), 2.93 (dd,
J = 5.0, 17.0 Hz, 1H), 4.55 (dt, J = 5.5, 7.0 Hz, 1H), 5.16 (d, J =
8.5 Hz, 1H), 7.10 (d, J = 8.0 Hz, 2H), 7.20–7.28 (m, 5H), 7.65
(d, J = 8.5 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 21.5, 26.2,
54.1, 116.3, 126.2, 127.1, 129.0, 129.2, 129.8, 136.4, 144.1;
HRMS (FAB): for C16H17N2O2S (M + H)+ calcd 301.1011,
found 301.1003.
N-(2-Chlorooctyl)-4-methylbenzenesulfonamide.4
(3c′). IR
(neat, cm−1) 3280, 2840, 1610; H NMR (500 Hz, CDCl3) δ
0.81 (t, J = 7.5 Hz, 3H), 1.10–1.25 (m, 8H), 1.39–1.47 (m, 1H),
1.51–1.57 (m, 1H), 2.40 (s, 3H), 3.40–3.52 (m, 3H), 4.91 (d, J =
8.5 Hz, m, 1H), 7.28 (d, J = 8.0 Hz, 2H), 7.75 (d, J = 8.0 Hz,
2H); 13C NMR (100 MHz, CDCl3) δ 14.0, 21.5, 22.4, 225, 25.2,
28.7, 31.4, 32.3, 48.1, 53.8, 127.0, 129.7, 137.8, 143.6; HRMS
(FAB): for C15H25ClNO2S (M + H)+ calcd 318.1295, found
318.1301.
1
N-(2-Cyano-1,2-diphenylethyl)-4-methylbenzenesulfonami-
1
de.5a (2g). IR (KBr, cm−1) 3270, 2960, 2100, 1600; H NMR
(500 Hz, CDCl3) δ 2.44 (s, 3H), 4.27 (s, 1H), 4.98 (br, 1H), 7.02
(d, J = 7.6 Hz, 2H), 7.07–7.13 (m, 3H), 7.25–7.42 (m, 7H), 7.81
(d, J = 7.6 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 21.4, 70.1,
126.4, 127.3, 127.4, 127.7, 128.1, 128.4, 129.3, 135.4, 136.9,
137.0, 142.9; Anal. Found: C, 69.90; H 5.20; N 7.79. Calcd for
C22H20N2O2S: C, 70.19; H 5.35; N 7.44%.
N-(2-Azidobutyl)-4-methylbenzenesulfonamide.4
(3d). IR
(neat, cm−1) 3280, 2100, 1600; H NMR (500 Hz, CDCl3) δ
0.74 (t, J = 7.0 Hz, 3H), 1.04–1.50 (m, 6H), 2.40 (s, 3H),
3.24–3.29 (m, 3H), 5.00 (brs, 1H), 7.28 (d, J = 8.0 Hz, 2H),
7.74 (d, J = 8.2 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 13.7,
21.5, 22.1, 27.5, 32.2, 53.2, 54.9, 126.9, 129.6, 137.6, 143.4;
HRMS (FAB): for C13H21N4O2S (M + H)+ calcd 297.1385,
found 297.1386.
1
N-(2-Azidocyclohexyl)-4-methylbenzenesulfonamide.4 (3a). IR
(KBr, cm−1) 3300, 2940, 2090, 1600; 1H NMR (500 Hz,
CDCl3) δ 1.12–1.33 (m, 4H), 1.54–1.68 (m, 2H), 1.92–2.00 (m,
2H), 2.39 (s, 3H), 2.91–2.95 (m, 1H), 3.07–3.10 (m, 1H), 5.29
(d, J = 8.0 Hz, 1H), 7.28 (d, J = 8.0 Hz, 2H), 7.78 (d, J =
8.0 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 21.5, 23.6, 23.8,
30.2, 32.4, 56.7, 63.5, 127.0, 129.5, 137.5, 143.3; HRMS (FAB):
for C13H19N4O2S (M + H)+ calcd 295.1229, found 295.1235.
N-(2-Azido-1-benzylethyl)-4-methylbenzenesulfonamide.6 (3e).
1
IR (neat, cm−1) 3270, 2090, 1600; H NMR (500 Hz, CDCl3) δ
2.39 (s, 3H), 2.68 (dd, J = 7.0, 14.0 Hz, 1H), 2.75 (dd, J = 7.5,
14.0 Hz, 1H), 3.28 (dd, J = 4.0, 12.0 Hz, 1H), 3.31 (dd, J = 6.5,
12.0 Hz, 1H), 3.45–3.54 (m, 1H), 4.92 (d, J = 8.0 Hz, 1H), 6.98
(d, J = 8.5 Hz, 2H), 7.10–7.35 (m, 5H), 7.60 (d, J = 8.5 Hz,
2H); 13C NMR (125 MHz, CDCl3) δ 21.5, 38.4, 53.7, 54.3,
126.8, 127.2, 128.6, 128.7, 129.1, 129.6, 136.1, 136.7, 143.4;
HRMS (FAB): for C16H19N4O2S (M + H)+ calcd 331.1229,
found 331.1236.
N-(2-Chlorocyclohexyl)-4-methylbenzenesulfonamide.4 (3a′).
IR (KBr, cm−1) 3270, 2860, 1920, 1600; 1H NMR (500 Hz,
CDCl3) δ 1.22–1.28 (m, 3H), 1.55–1.67 (m, 3H), 2.10–2.15 (m,
2H), 2.39 (s, 3H), 3.05–3.10 (m, 1H), 3.66–3.69 (m, 1H), 5.20
(d, J = 6.0 Hz, 1H), 7.26 (d, J = 8.0 Hz, 2H), 7.75 (d, J =
8.0 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 21.5, 23.4, 24.3,
32.4, 34.9, 58.7, 62.1, 127.3, 129.6, 137.2, 143.4; HRMS (FAB):
for C13H19ClNO2S (M + H)+ calcd 288.0825, found 288.0833.
N-(2-Chloro-1-benzylethyl)-4-methylbenzenesulfonamide.6
(3e′). IR (neat, cm−1) 3270, 2890, 1600; 1H NMR (500 Hz,
CDCl3) δ 2.40 (s, 3H), 2.75 (dd, J = 6.5, 13.5 Hz, 1H), 2.87 (dd,
J = 7.5, 13.5 Hz, 1H), 3.43 (dd, J = 5.5, 11.5 Hz, 1H), 3.47 (dd,
J = 3.0, 11.5 Hz, 1H), 3.64–3.71 (m, 1H), 4.88 (d, J = 7.0 Hz,
1H), 7.03 (d, J = 7.5 Hz, 2H), 7.17–7.22 (m, 5H), 7.61 (d, J =
8.5 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 21.5, 38.2, 46.8,
55.1, 126.9, 127.0, 128.7, 128.8, 129.1, 129.7, 136.1, 137.2,
143.5; HRMS (FAB): for C16H19ClNO2S (M + H)+ calcd
324.0825, found 324.0830.
N-(2-Bromocyclohexyl)-4-methylbenzenesulfonamide.4 (3a′′).
IR (KBr, cm−1) 3270, 2870, 1900, 1610; 1H NMR (500 Hz,
CDCl3) δ 1.23–1.30 (m, 3H), 1.58–1.64 (m, 2H), 1.71–1.79 (m,
1H), 2.18–2.28 (m, 2H), 2.40 (s, 3H), 3.14–3.19 (m, 1H),
3.80–3.88 (m, 1H), 5.11 (d, J = 5.5 Hz, 1H), 7.28 (d, J = 8.0 Hz,
2H), 7.76 (d, J = 8.0 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ
21.5, 23.4, 25.3, 32.8, 35.7, 55.0, 58.6, 127.3, 129.6, 137.1,
143.5; HRMS (FAB): for C13H19BrNO2S (M + H)+ calcd
332.0320, found 332.0323.
N-(2-Bromo-1-benzylethyl)-4-methylbenzenesulfonamide.6
1
(3e′′). IR (neat, cm−1) 3250, 2850, 1590; H NMR (500 Hz,
N-(2-Azidocyclopentyl)-4-methylbenzenesulfonamide.4 (3b).
IR (KBr, cm−1) 3260, 2960, 2100, 1600; 1H NMR (500 Hz,
CDCl3) δ 1.31–1.39 (m, 1H), 1.51–1.65 (m, 3H), 1.81–1.92 (m,
2H), 2.40 (s, 3H), 3.36 (dt, J = 5.0, 7.0 Hz, 1H), 3.65–3.71
(m, 1H), 5.54 (d, J = 8.0 Hz, 1H), 7.28 (d, J = 8.0 Hz, 2H), 7.76
(d, J = 8.0 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 20.8,
21.5, 26.9, 29.0, 30.8, 59.7, 66.9, 126.7, 129.6, 137.0, 143.5;
HRMS (FAB): for C12H17N4O2S (M + H)+ calcd 281.1072,
found 281.1075.
CDCl3) δ 2.39 (s, 3H), 2.73 (dd, J = 5.5, 14.0 Hz, 1H), 2.87 (dd,
J = 8.0, 14.0 Hz, 1H), 3.31 (dd, J = 5.5, 11.0 Hz, 1H), 3.34 (dd,
J = 5.0, 11.0 Hz, 1H), 3.57–3.62 (m, 1H), 5.02 (d, J = 8.0 Hz,
1H), 7.01–7.08 (m, 2H), 7.15–7.22 (m, 5H), 7.62 (d, J = 8.5 Hz,
2H); 13C NMR (125 MHz, CDCl3) δ 21.4, 37.4, 41.1, 54.6,
126.9, 127.0, 128.6, 129.1, 129.5, 129.8, 136.0, 137.1, 143.4;
HRMS (FAB): for C16H19BrNO2S (M + H)+ calcd 368.0320,
found 368.0318.
N-(2-Azidooctyl)-4-methylbenzenesulfonamide.4
(3c). IR
N-(2-Azido-1-phenylethyl)-4-methylbenzenesulfonamide.4
(3f). IR (KBr, cm−1) 3280, 2100, 1590 (mixture of 3f and 4f);
(neat, cm−1) 3280, 2940, 2100, 1600; 1H NMR (500 Hz,
This journal is © The Royal Society of Chemistry 2012
Org. Biomol. Chem., 2012, 10, 4886–4890 | 4889

1H NMR (500 Hz, CDCl3) δ 2.37 (s, 3H), 3.53 (d, J = 6.5 Hz,
1H), 4.47 (dd, J = 6.0, 16.5 Hz, 1H), 5.62 (d, J = 8.0 Hz, 1H),
7.10 (d, J = 8.0 Hz, 2H), 7.18–7.38 (m, 5H), 7.60 (d, J =
8.0 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 21.4, 55.9, 57.1,
126.7, 127.0, 128.1, 128.6, 129.4, 137.0, 137.5, 143.4; HRMS
(FAB): for C15H17N4O2S (M + H)+ calcd 317.1072, found
317.1075 (mixture of 3f and 4f).
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N-(2-Azido-2-phenylethyl)-4-methylbenzenesulfonamide.4
(4f). IR (KBr, cm−1) 3280, 2100, 1590 (mixture of 3f and 4f);
1H NMR (400 Hz, CDCl3) δ 2.43 (s, 3H), 3.06 (ddd, J = 5.0,
8.0, 13.5 Hz, 1H), 3.21 (ddd, J = 5.0, 7.5, 13.5 Hz, 1H), 4.60
(dd, J = 5.5, 9.0 Hz, 1H), 5.11 (dd, J = 5.5, 7.5 Hz, 1H), 7.18 (d,
J = 8.0 Hz, 2H), 7.18–7.38 (m, 5H), 7.72 (d, J = 8.0 Hz, 2H);
13C NMR (125 MHz, CDCl3) δ 21.5, 48.0, 65.4, 126.9, 127.0,
128.9, 129.0, 129.8, 136.2, 136.7, 143.7.
N-(2-Azido-1,2-diphenylethyl)-4-methylbenzenesulfonamide.5e
1
(3g). IR (KBr, cm−1) 3270, 2960, 2100, 1600; H NMR (400
Hz, CDCl3) δ 2.31 (s, 3H), 4.48–4.51 (m, 1H), 4.69 (d, J = 6.5
Hz, 1H), 5.53 (brs, 1H), 6.94 (d, J = 7.0 Hz, 2H), 7.01 (d, J =
8.0 Hz, 2H), 7.05–7.15 (m, 5H), 7.20–7.24 (m, 3H), 7.38 (d, J =
8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 21.4, 62.3, 70.2,
126.9, 127.4, 127.5, 127.8, 128.1, 128.6, 129.2, 135.4, 136.9,
137.0, 143.0; HRMS (FAB): for C21H21N4O2S (M + H)+ calcd
393.1385, found 393.1377.
N-(2-Chloro-1,2-diphenylethyl)-4-methylbenzenesulfonamide
(3g′). IR (KBr, cm−1) 3250, 2960, 2880, 1600; 1H NMR
(400 Hz, CDCl3) δ 2.32 (s, 3H), 4.72 (t, J = 6.5 Hz, 1H), 5.00
(d, J = 6.5 Hz, 1H), 5.39 (d, J = 6.0 Hz, 1H), 6.90 (d, J = 7.0 Hz,
2H), 7.02–7.06 (m, 4H), 7.08–7.15 (m, 2H), 7.16–7.21 (m, 4H),
7.38 (d, J = 7.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 21.5,
63.8, 66.8, 127.1, 127.9, 1280, 128.3, 128.7, 129.2, 136.5,
136.9, 136.9, 143.2.; HRMS (FAB): for C21H21ClNO2S
(M + H)+ calcd 386.0982, found 386.0988.
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4890 | Org. Biomol. Chem., 2012, 10, 4886–4890
This journal is © The Royal Society of Chemistry 2012