TTMPP: An efficient organocatalyst in the ring-opening of aziridines with silylated nucleophiles

Article abstract of DOI:10.1039/b908322g

The ring-opening of N-tosylaziridines with silylated nucleophiles catalyzed by tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP) afforded the corresponding β-functionalized sulfonamides in excellent yield under mild reaction conditions.

Full text of DOI:10.1039/b908322g

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www.rsc.org/obc | Organic & Biomolecular Chemistry
TTMPP: An efficient organocatalyst in the ring-opening of aziridines with
silylated nucleophiles†
Satoru Matsukawa* and Kumiko Tsukamoto
Received 27th April 2009, Accepted 27th May 2009
First published as an Advance Article on the web 16th July 2009
DOI: 10.1039/b908322g
The ring-opening of N-tosylaziridines with silylated nucleophiles catalyzed by
tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP) afforded the corresponding b-functionalized
sulfonamides in excellent yield under mild reaction conditions.
Table 1 Optimization of the reaction conditions
Introduction
Aziridines are very useful intermediates for the synthesis of
numerous nitrogen-containing, biologically active compounds.1
Therefore, nucleophilic ring-opening of aziridines has been widely
examined and developed.2 Among these approaches, the ring-
opening reaction using silylated nucleophiles, such as silyl cyanide,
Entry
Phosphine
Solvent
Yield (%)
azide or halides, is an important approach to produce highly
functionalized compounds. Therefore, the catalytic ring-opening
reaction with silylated nucleophiles using Lewis acids3 and fluoride
ion4 has been developed to realize high yields and selectivities.
However, when compared to other silylated nucleophiles, examples
of catalytic ring-opening of aziridines with silyl cyanide remain
scarce, although the resulting b-amino nitriles are easily con-
verted to 1,3-diamines and b-amino acids.5 Recently, Lewis base-
catalyzed reactions have also been reported. Komatsu reported
that N,N,N¢,N¢-tetramethylethylenediamine (TMEDA) acts as a
Lewis base catalyst in this ring-opening reaction with various sily-
lated nucleophiles.6 However, in the reaction with silylcyanide, the
presence of toxic KCN was required for high yields. Furthermore,
catalyst loading is high and reactions usually needed a long time
for completion. Although DMF,7a N-heterocyclic carbenes7b and
DMSO7c also act as good promoters or catalysts, examples of
them are limited in reactions with reactive silylated nucleophiles.
In search of a broadly applicable reaction, we planned to use
a highly basic phosphine, tris(2,4,6-trimethoxyphenyl)phosphine
(TTMPP),8 as a Lewis base catalyst.
1
2a
3b
4
TTMPP
TTMPP
TTMPP
TTMPP
TTMPP
TTMPP
TMPPd
Ph3P
DMF
DMF
DMF
THF
Toluene
MeCN
DMF
DMF
DMF
DMF
98
86
50
77
34
51
35
30
5c
6c
7
8
9
10
nBu3P
None
50
trace
a 2 mol% of TTMPP was used. b The reaction was carried out at
room temperature. c The reaction was carried out for 24 h. d Tris(4-
methoxyphenyl)phosphine.
Results and discussion
Initially, the ring-opening reaction of N-tosylaziridine 1a with
trimethylsilyl cyanide was examined in the presence of 10 mol%
of TTMPP in DMF at 50 C. The reaction proceeded smoothly
◦
and the desired product was obtained at 98% yield in 4 h (Table 1,
entry 1). This reaction also proceeded smoothly when 2 mol%
of TTMPP was used. The product was obtained in moderate to
low yield when other phosphines, such as triphenylphosphine,
tributylphosphine12 and TMPP, were used instead of TTMPP
(Table 1, entries 1 vs. 7–9). Without catalyst, only trace amounts of
the products were obtained. The reactions performed in MeCN,
THF and toluene were inferior to the reaction in DMF.
Tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP) is known to
be a highly basic phosphine owing to its methoxy substitutents.
Based on this property, some unique catalytic reactions have been
reported.9 We have also reported that TTMPP acts as a good Lewis
base catalyst in the reaction with silylated nucleophiles via O–Si
and C–Si bond activation.10 In an effort to apply this phosphine to
other useful reactions, we examined the ring-opening of aziridines
with trimethylsilyl cyanide11 and other silylated nucleophiles.
In order to clarify the scope of this reaction, several N-
tosylaziridines were examined in the presence of 10 mol%
TTMPP. Good results were obtained for both 2-substituted
aziridines and 2,3-disubstituted aziridines. High yields of the
corresponding product were obtained using bicyclic aziridine and
alkyl-substituted aziridines (Table 2, entries 1–7). In the case of 2-
substituted N-tosylaziridines, reaction also proceeded smoothly
when 2 mol% TTMPP was used (Table 2, entries 5 and 7).
Furthermore, complete regioselectivity with nucleophilic attack
on the less substituted carbon was observed (Table 2, entries 3–8).
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: 1H and 13C NMR
spectra. See DOI: 10.1039/b908322g
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Table 2 TTMPP-catalyzed ring-opening of various aziridines with
Me3SiCN
Table 3 TTMPP-catalyzed ring-opening of aziridines with other silylated
nucleophiles
Entry Aziridine
1
Product
Time Yield (%)a
Entry
1
Aziridine
Nu
N3
Product
Time Yield (%)a,b
4 h
98
1a
3 h
98 (3a)
2
1a
Cl
3 h
88 (3a¢)
2
3
9 h
3 h
99
88
3
4
1b
1b
N3
Cl
6 h
4 h
95 (3b)
83 (3b¢)
4
3 h
6 h
91
82
5b
5
6
7
1c
1d
1d
N3
N3
Cl
5 h
95 (3c)
98 (3d)
96 (3d¢)
6
1 h
4 h
92
88
7b
3 h
8
9
3 h
50
1.5 h
24 h
Trace
8
9
1e
1f
N3
N3
1 h
2 h
89 (3e)
93 (3f, 4f)c
10c
24 h
68
10
1g
N3
12 h
95 (3g)
a Isolated yield. b 2 mol% of TTMPP was used. c The reaction was carried
out at 100 ◦C.
11d
12
1g
1h
N3
N3
12 h
12 h
Trace
77 (3h)
Unfortunately, in the case of phenyl-substituted aziridine 1f, the
yield was unsatisfactory owing to the occurrence of elimination of
the N-tosyl group from the product. Moderate to low yields of the
product were obtained using 2,3-diphenylaziridine, possibly due
to steric inhibition.
This TTMPP-catalyzed reaction is also applicable to other
silylated nucleophiles, trimethylsilyl azides and halides (Table 3).
Although the reaction can proceed without catalyst at high tem-
peratures in some cases, this TTMPP-catalyzed reaction proceeded
smoothly at room temperature in shorter times with higher yields.
High yields of the corresponding product were obtained using
13d
1h
N3
12 h
Trace
a Isolated yield. b The product was 3a–h unless otherwise noted.
c Regioisomer ratio 3f : 4f = 21 : 79. d The reaction was carried out without
catalyst.
both 2-substituted aziridines and 2,3-disubstituted aziridines. 2,3-
Diphenylaziridine also gave good results. Almost complete regios-
electivity was observed when using alkyl-substituted aziridines
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as substrates. However, for phenyl-substituted aziridine 1f, the
regioselectivity was not satisfactory due to electronic effects.
A possible mechanism is illustrated in Scheme 1. Hou proposed
phosphonium intermediate A (produced from phosphine and
aziridine) as an active species in the tributylphosphine-catalyzed
ring-opening reaction of aziridines with phenols, thiols and
amines.12a However, this species could not confirmed by 1H NMR
analysis with the 1:1 mixture of TTMPP and aziridine 1a in DMF-
d7. We thus propose the following alternative mechanism. First,
TTMPP coordinates the silicon atom of the silylated nucleophile
to form activated hexa-coordinated silicon species B (mainly in
DMF) or penta-coordinated silicon species B¢, with the C–Si bond
being activated. The nucleophilicity of the silylated nucleophile is
thus enhanced, and it readily reacts with an electrophile to produce
an amino ion and silylphosphonium salt. Finally, immediate
silylation occurs to give the silylated adduct with regeneration
of TTMPP.
used as received without further purification. The aziridines were
prepared according to a literature procedure.13
General procedure
To a solution of TTMPP (0.05 mmol) in DMF (1 mL) was added
aziridine (0.5 mmol◦) and silylated nucleophile (0.75 mmol) at room
temperature or 50 C. After the reaction was complete (checked
by TLC), the resultant mixture was quenched with water (2 mL).
The mixture was extracted with EtOAc and the organic layer was
washed with brine, dried over anhydrous Na2SO4, and evaporated.
The crude mixture was purified by preparative TLC to afford the
corresponding product.
N-(2-Cyanocyclohexyl)-4-methylbenzenesulfonamide4 (2a). IR
(KBr, cm-1) 3250, 2250, 1620; 1H NMR (400 Hz, CDCl3) d 1.28 (m,
3H), 1.58 (m, 3H), 1.84 (m, 1H), 2.04 (m, 1H), 2.43 (s, 3H), 2.66
(m, 1H), 3.37 (m, 1H), 5.73 (d, J = 8.0 Hz, 1H), 7.32 (d, J = 8.1 Hz,
2H), 7.82 (d, J = 8.1 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 21.7,
22.6, 23.2, 27.8, 30.9, 34.4, 52.5, 120.4, 127.2, 129.3, 137.0, 144.0;
Anal. Found: C, 60.56; H 6.67; N 9.96. Calc. for C14H18N2O2S: C,
60.41; H 6.52; N 10.06%.
N-(2-Cyanocyclopentyl)-4-methylbenzenesulfonamide4
(2b).
IR (KBr, cm-1) 3260, 2250, 1600; H NMR (400 Hz, CDCl3) d
1.48 (m, 1H), 1.72 (m, 2H), 1.88 (m, 1H), 1.99 (m, 1H), 2.08 (m,
1H), 2.45 (s, 3H), 2.83 (dt, J = 6.0, 8.8 Hz, 1H), 3.76 (m, 1H),
5.03 (m, 1H), 7.34 (d, J = 8.0 Hz, 2H), 7.81 (d, J = 8.0 Hz, 2H);
13C NMR (100 MHz, CDCl3) d 21.7, 22.6, 28.8, 31.9, 35.4, 58.5,
121.0, 126.9, 129.6, 137.4, 143.9; Anal. Found: C, 58.82; H 6.07;
N 10.49. Calc. for C13H16N2O2S: C, 59.07; H 6.10; N 10.60%.
1
N-(2-Cyanooctyl)-4-methylbenzenesulfonamide4
(2c). IR
(neat, cm-1) 3310, 2250, 1600; H NMR (400 Hz, CDCl3) d 0.83
(t, J = 6.8 Hz, 3H), 1.07–1.30 (m, 8H), 1.52 (m, 2H), 2.44 (s, 3H),
2.54 (dd, J = 4.1, 17.2 Hz, 1H), 2.64 (dd, J = 6.4, 17.2 Hz, 1H),
3.42 (m, 1H), 4.95 (m, 1H), 7.33 (d, J = 8.0 Hz, 2H), 7.78 (d, J
= 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 14.1, 21.7, 22.6,
25.0, 25.2, 28.8, 31.4, 33.4, 50.5, 116.6, 127.0, 129.5, 137.5, 144.0;
Anal. Found: C, 61.92; H 7.93; N 8.90. Calc. for C16H24N2O2S: C,
62.30; H 7.84; N 9.08%.
1
Scheme 1 Proposed mechanism.
N-(2-Cyanobutyl)-4-methylbenzenesulfonamide4
(2d). IR
(neat, cm-1) 3270, 2240, 1600; H NMR (400 Hz, CDCl3) d 0.85
(t, J = 6.8 Hz, 3H), 1.08–1.31 (m, 4H), 1.51 (m, 2H), 2.44 (s, 3H),
2.55 (dd, J = 4.0, 17.2 Hz, 1H), 2.65 (dd, J = 6.0, 17.2 Hz, 1H),
3.42 (m, 1H), 4.93 (m, 1H), 7.32 (d, J = 8.0 Hz, 2H), 7.78 (d, J =
8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 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,
60.16; H 7.28; N 9.90. Calc. for C14H20N2O2S: C, 59.97; H 7.19;
N 9.99%.
1
Conclusions
In conclusion, we have demonstrated that TTMPP catalyzes
ring-opening of aziridines with silylated nucleophiles. A broad
range of silyl nucleophiles, including silyl cyanide, azide and
halides, can be applied under mild conditions using 2–10 mol%
TTMPP. This reaction provides a simple route to the synthesis
of highly functionalized b-amino acids, 1,2-diamines and 1,3-
diamines.
N-(2-Cyano-1-benzylethyl)-4-methylbenzenesulfonamide6 (2e).
1
IR (neat, cm-1) 3270, 2250, 1600; H NMR (400 Hz, CDCl3) d
Experimental
2.42 (s, 3H), 2.56 (dd, J = 4.0, 16.4 Hz, 1H), 2.66 (dd, J = 6.0,
16.4 Hz, 1H), 2.77 (dd, J = 7.6, 14.0 Hz, 1H), 2.90 (dd, J = 6.8,
14.0 Hz, 1H), 3.64 (m, 1H), 4.82 (m, 1H), 6.98 (d, J = 7.6 Hz,
2H), 7.20 (m, 5H), 7.55 (d, J = 8.4 Hz, 2H); 13C NMR (100 MHz,
CDCl3) d 21.7, 24.1, 39.8, 51.0, 116.6, 126.8, 127.2, 128.4, 128.6,
129.7, 134.2, 136.2, 143.5; Anal. Found: C, 64.68; H 5.74; N 8.80.
Calc. for C17H18N2O2S: C, 64.94; H 5.77; N 8.91%.
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 Chemicals. Other commercially available reagents was
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N-(2-Chlorobutyl)-4-methylbenzenesulfonamide7a
N-(2-Cyano-1-phenylethyl)-4-methylbenzenesulfonamide4 (2f).
(3d¢). IR
1
1
IR (KBr, cm-1) 3280, 2250, 1590; H NMR (400 Hz, CDCl3) d
(neat, cm-1) 3270, 2850, 1610; H NMR (400 Hz, CDCl3) d 0.76
(t, J = 7.2 Hz, 3H), 1.10–1.50 (m, 6H), 2.42 (s, 3H), 3.33 (m, 3H),
5.10 (br, 1H), 7.30 (d, J = 8.2 Hz, 2H), 7.81 (d, J = 8.2 Hz, 2H);
Anal. Found: C, 54.02; H 6.65; N 5.12. Calc. for C12H16ClNO2S:
C, 53.87; H 6.96; N 4.83%.
2.43 (s, 3H), 2.87 (dd, J = 7.6, 17.2 Hz, 1H), 2.93 (dd, J = 6.0,
17.2 Hz, 1H), 4.57 (m, 1H), 5.40 (br, 1H), 7.10 (d, J = 8.0 Hz,
2H), 7.28 (m, 5H), 7.65 (d, J = 8.4 Hz, 2H); 13C NMR (100 MHz,
CDCl3) d 21.1, 26.3, 54.1, 116.6, 126.0, 127.2, 128.6, 128.9, 129.7,
136.2, 136.9, 143.5; Anal. Found: C, 64.22; H 5.45; N 9.48. Calc.
for C16H16N2O2S: C, 63.98; H 5.37; N 9.33%.
N-(2-Azido-1-benzylethyl)-4-methylbenzenesulfonamide6 (3e).
1
IR (neat, cm-1) 3270, 2090, 1600; H NMR (400 Hz, CDCl3) d
2.42 (s, 3H), 2.72 (dd, J = 7.0, 11.2 Hz, 2H), 3.32 (dd, J = 4.4,
12.4 Hz, 1H), 3.54 (m, 1H), 5.00 (br, 1H), 6.98 (d, J = 8.0 Hz,
2H), 7.20 (m, 5H), 7.58 (d, J = 8.4 Hz, 2H); 13C NMR (100 MHz,
CDCl3) d 21.4, 38.8, 53.7, 54.4, 126.8, 127.2, 128.4, 128.6, 129.0,
129.5, 136.0, 136.7, 143.3.
N-(2-Cyano-2-ethylbutyl)-4-methylbenzenesulfonamide
(2h).
Obtained as a colorless viscous oil after preparative TLC (Rf =
0.26 in Hex/AcOEt = 1/1); IR (neat, cm-1) 3270, 2250, 1600;
1H NMR (400 Hz, CDCl3) d 0.72 (t, J = 7.2 Hz, 3H), 1.04 (t,
J = 6.8 Hz, 3H), 1.47 (m, 2H), 1.59 (m, 2H), 2.43 (s, 3H), 2.75
(td, J = 4.8, 6.0 Hz, 1H), 3.21 (td, J = 4.8, 5.2 Hz, 1H), 4.65
N-(2-Azido-1-phenylethyl)-4-methylbenzenesulfonamide4 (3f).
(br, 1H), 7.32 (d, J = 7.2 Hz, 2H), 7.75 (d, J = 7.2 Hz, 2H); 13
C
1
IR (KBr, cm-1) 3280, 2100, 1590; H NMR (400 Hz, CDCl3) d
NMR (100 MHz, CDCl3) d 9.9, 12.1, 21.6, 23.0, 23.8, 40.9, 55.8,
119.6, 126.9, 129.8, 137.4, 143.8; Anal. Found: C, 60.08; H 7.08;
N 10.06. Calc. for C14H20N2O2S: C, 59.97; H 7.19; N 9.99%.
2.37 (s, 3H), 3.56 (d, J = 6.0 Hz, 1H), 4.45 (m, 1H), 5.40 (br, 1H),
7.10 (d, J = 8.0 Hz, 2H), 7.20 (m, 5H), 7.61 (d, J = 8.4 Hz, 2H).
N-(2-Azido-2-phenylethyl)-4-methylbenzenesulfonamide4 (4f).
N-(2-Azidocyclohexyl)-4-methylbenzenesulfonamide4 (3a). IR
(KBr, cm-1) 3300, 2940, 2090, 1600; 1H NMR (400 Hz, CDCl3) d
1.20–1.30 (m, 4H), 1.60–1.70 (m, 2H), 2.02 (m, 2H), 2.43 (s, 3H),
2.93 (m, 1H), 3.09 (m, 1H), 5.09 (m, 1H), 7.31 (d, J = 8.4 Hz, 2H),
7.80 (d, J = 8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 21.5,
23.6, 23.8, 30.2, 32.4, 59.0, 63.5, 127.0, 129.5, 137.5, 143.2.
1
IR (KBr, cm-1) 3280, 2100, 1590; H NMR (400 Hz, CDCl3) d
2.43 (s, 3H), 3.07 (ddd, J = 4.4, 4.8, 9.2 Hz, 1H), 3.20 (ddd, J =
2.8, 4.4, 9.2 Hz, 1H), 4.59 (dd, J = 5.6, 8.8 Hz, 1H), 4.95 (br, 1H),
7.15 (d, J = 8.0 Hz, 2H), 7.20 (m, 5H), 7.73 (d, J = 8.4 Hz, 2H).
N -(2-Azido-1,2-diphenylethyl)-4-methylbenzenesulfonamide14
(3g). IR (KBr, cm-1) 3270, 2960, 2100, 1600; 1H NMR (400 Hz,
CDCl3) d 2.40 (s, 3H), 4.61 (t, J = 6.8 Hz, 1H), 4.80 (d, J = 6.0 Hz,
1H), 5.69 (d, J = 6.8 Hz, 1H), 7.02 (d, J = 7.6 Hz, 2H), 7.09 (d,
J = 8.0 Hz, 2H), 7.19 (m, 5H), 7.32 (d, J = 8.0 Hz, 2H), 7.49 (d,
J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 21.4, 62.3, 70.1,
126.8, 127.3, 127.4, 127.7, 128.0,128.4, 129.1, 135.4, 136.9, 137.0,
142.9; HRMS: for C21H20NO2S (M - N3)+ calcd 350.1215, found
350.1212.
N-(2-Chlorocyclohexyl)-4-methylbenzenesulfonamide4
(3a¢).
IR (KBr, cm-1) 3270, 2860, 1920, 1600; 1H NMR (400 Hz, CDCl3)
d 1.28 (m, 3H), 1.62 (m, 3H), 1.84 (m, 1H), 2.04 (m, 1H), 2.41
(s, 3H), 3.15 (m, 1H), 3.66 (m, 1H), 4.85 (br, 1H), 7.32 (d, J =
8.0 Hz, 2H), 7.78 (d, J = 8.0 Hz, 2H); Anal. Found: C, 54.04; H
6.11; N 5.00. Calc. for C13H18ClNO2S: C, 54.25; H 6.30; N 4.87%.
N-(2-Azidocyclopentyl)-4-methylbenzenesulfonamide4
(3b).
IR (KBr, cm-1) 3260, 2960, 2100, 1600; 1H NMR (400 Hz, CDCl3)
d 1.40 (m, 1H), 1.62 (m, 3H), 1.92 (m, 2H), 2.43 (s, 3H), 3.38
(dt, J = 5.2, 5.6 Hz, 1H), 3.71 (m, 1H), 5.45 (m, 1H), 7.32 (d, J
= 8.0 Hz, 2H), 7.80 (d, J = 8.0 Hz, 2H);13C NMR (100 MHz,
CDCl3) d 20.8, 21.5, 26.9, 29.0, 30.8, 59.7, 66.9, 126.7, 129.6,
137.0, 143.5.
N-(2-Azido-2-ethylbutyl)-4-methylbenzenesulfonamide
(3h).
Obtained as a white solid after preparative TLC (Rf = 0.67 in
◦
Hex/AcOEt = 1/1); mp 78–79 C; IR (KBr, cm-1) 3240, 2090,
1600; 1H NMR (400 Hz, CDCl3) d 0.73 (t J = 7.6 Hz, 3H), 0.92 (t
J = 7.4 Hz, 3H), 1.30(m, 2H), 1.53 (m, 2H), 2.43 (s, 3H), 3.17–3.27
(m, 2H), 4.83 (d, J = 8.8 Hz, 1H), 7.30 (d, J = 8.0 Hz, 2H), 7.77
(d, J = 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 10.2, 11.0,
21.5, 21.8, 24.4, 58.1, 67.8, 126.9, 129.3, 137.9, 143.4; HRMS: for
C13H20NO2S (M - N3)+ calcd 254.1215, found 254.1220.
N-(2-Chlorocyclopentyl)-4-methylbenzenesulfonamide4
(3b¢).
IR (KBr, cm-1) 3260, 2890, 1600; H NMR (400 Hz, CDCl3) d
1.41 (m, 1H), 1.60 (m, 3H), 1.92 (m, 2H), 2.41 (s, 3H), 3.55 (m,
1H), 4.10 (m, 1H), 4.80 (m, 1H), 7.33 (d, J = 8.0 Hz, 2H), 7.81 (d,
J = 8.0 Hz, 2H); Anal. Found: C, 52.80; H 6.05; N 5.12. Calc. for
C12H16ClNO2S: C, 52.64; H 5.89; N 5.12%.
1
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(c) W.-H. Leung, M. T. Yu, M. C. Wu and L.-L. Yeung, Tetrahedron
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N-(2-Azidooctyl)-4-methylbenzenesulfonamide4
(3c). IR
(neat, cm-1) 3280, 2940, 2100, 1600; 1H NMR (400 Hz, CDCl3) d
0.85 (t, J = 7.2 Hz, 3H), 1.10–1.55 (m, 10H), 2.43 (s, 3H), 3.30 (m,
3H), 4.86 (m, 1H), 7.30 (d, J = 8.0 Hz, 2H), 7.76 (d, J = 8.0 Hz,
2H); 13C NMR (100 MHz, CDCl3) d 14.0, 21.6, 22.5, 25.4, 28.8,
31.6, 32.6, 53.2, 55.0, 127.0, 129.6, 137.0, 143.5.
N-(2-Azidobutyl)-4-methylbenzenesulfonamide4
(3d). IR
(neat, cm-1) 3280, 2100, 1600; H NMR (400 Hz, CDCl3) d 0.74
(t, J = 7.0 Hz, 3H), 1.14–1.55 (m, 6H), 2.42 (s, 3H), 3.28 (m, 3H),
5.00 (m, 1H), 7.30 (d, J = 8.2 Hz, 2H), 7.76 (d, J = 8.2 Hz, 2H);
13C NMR (100 MHz, CDCl3) d 13.7, 21.5, 22.1, 27.5, 32.2, 53.2,
54.8, 126.9, 129.6, 137.6, 143.4.
1
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3796 | Org. Biomol. Chem., 2009, 7, 3792–3796
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