Transformation of allyl stannanes into allyl amines using [N-(p-toluenesulfonyl)imino]-phenyliodinane

Article abstract of DOI:10.1081/SCC-100105125

Reaction of allyl stannanes with PhI = NTs in the presence of 10mol % of Cu(OTf)₂ provides a direct route for the preparation of N-tosylallyl amines in moderate yields.

Full text of DOI:10.1081/SCC-100105125

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TRANSFORMATION OF ALLYL STANNANES INTO ALLYL
AMINES USING [N-(p-TOLUENESULFONYL)IMINO]-
PHENYLIODINANE
Dae Young Kim a , Hee Suk Kim a , Young Jae Choi a , Joo Yang Mang a & Kilsung Lee b
a Department of Chemistry , Soonchunhyang University , Asan P.O. Box 97, Chungnam,
336-600, Korea
b Cheil Industries Inc. , Euiwang, Kyoungki, 437-010, Korea
Published online: 09 Nov 2006.
To cite this article: Dae Young Kim , Hee Suk Kim , Young Jae Choi , Joo Yang Mang & Kilsung Lee (2001) TRANSFORMATION
OF ALLYL STANNANES INTO ALLYL AMINES USING [N-(p-TOLUENESULFONYL)IMINO]-PHENYLIODINANE, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:16, 2463-2469,
DOI: 10.1081/SCC-100105125
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SYNTHETIC COMMUNICATIONS, 31(16), 2463–2469 (2001)
TRANSFORMATION OF ALLYL
STANNANES INTO ALLYL AMINES
USING [N-( p-TOLUENESULFONYL)IMINO]-
PHENYLIODINANE
Dae Young Kim,1, Hee Suk Kim,1 Young Jae Choi,1
*
Joo Yang Mang,1 and Kilsung Lee2
1Department of Chemistry, Soonchunhyang University,
Asan P.O. Box 97, Chungnam 336-600, Korea
2Cheil Industries Inc., Euiwang, Kyoungki 437-010, Korea
ABSTRACT
Reaction of allyl stannanes with PhI ¼ NTs in the presence of
10 mol % of Cu(OTf )2 provides a direct route for the pre-
paration of N-tosylallyl amines in moderate yields.
The preparation of allyl amines has been an area of considerable activ-
ity in recent years due primarily to their key function as intermediates in
organic synthesis,1 as well as their biological properties2 and their presence
in several natural products.3 A number of synthetic methods for the prepara-
tion of allyl amines from alkene derivatives have been developed, but these
require severe reaction conditions or several sequential reactions.4 Synthetic
methods for the preparation of allyl amines by nucleophilic allylic substitu-
tions such as amination of allyl alcohols,5 the Gabriel synthesis,6 amination
of allyl halides or acetates catalyzed by Pd,7 Rh,8 Ir,9 etc, complexes, or direct
*Corresponding author. E-mail: dyoung@sch.ac.kr
2463
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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2464
KIM ET AL.
amination of dienes and allenes10 met with varying degrees of success in the
construction of allylic amines. Allyl amines were also obtained by allylic
oxidation of simple alkenes using diimido- or imidoselenium reagents,11
diimido-or imidosulfur reagent,12 azodicarboxylates,13 [N-(p-toluenesulfony-
l)imino]phenyliodinane,14 acyl nitroso compounds,15 N-sulfinylcarbonate,16
molybdenum oxaziridines,17 peroxycarbamate,18 catalytic molybdenum19 or
iron20 complex as the catalysts and N-phenylhydroxyamine, as the nitrogen
fragment donor. Other miscellaneous methods include amination of allyl
phenyl tellurides with [N-(p-toluenesulfonyl)imino]phenyliodinane or chlor-
amine-T,21 the reaction of amine with allyl phenyl telluroxide which was
prepared from allyl silane and benzenetellurinyl trifluoroacetate,22 and the
reaction of allyl silanes with (ethoxycarbonyl)nitrene.23
We have already demonstrated the transformation of allyl silanes into
allyl amines using [N-(p-toluenesulfonyl)imino]phenyliodinane (PhI ¼ NTs)
as aminating agent.24 We report here the preparation of allyl amines from
allyl stannanes using PhI ¼ NTs in the presence of Cu(OTf)2 at room tem-
perature. Amination of allyl stannanes with PhI ¼ NTs did not proceed in the
absence of Cu(OTf)2. In the presence of 10 mol % of Cu(OTf)2, a slight
excess of the PhI ¼ NTs (1.5 equiv.) reacted with allyl stannanes (the stoichio-
metrically limiting component except in entry 3) to form the N-tosylallyl
amines. As shown in Table 1, the yields are moderate. Small amounts of
the p-toluenesulfonamide were observed as contaminents. This is thought
to arise from the decomposition of PhI ¼ NTs under the reaction conditions.
The reaction carried out in acetonitrile is much faster than in benzene (entries
1–3). The use of 10 mol % of Cu(OTf)2 in acetonitrile at room temperature
was found to be the optimal catalyst load-solvent combination for the amina-
tion of allyl stannanes using PhI ¼ NTs.
In summary, we have developed a new synthetic method for the
preparation of allyl amines from allyl stannanes using PhI ¼ NTs in the
presence of Cu(OTf )2 as the catalyst.
EXPERIMENTAL
All reactions were carried out under nitrogen atmosphere. Acetonitrile
and benzene were distilled from calcium hydride and stored over 4Aꢀ

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TRANSFORMATION OF ALLYL STANNANES
Table 1. Preparation of Allyl Amine from Stannes
2465
1
molecular sieves. H and 13C NMR were measured at 200 and 50 MHz
respectively, in CDCl3 with TMS as internal standard. Mass spectra were
recorded on Shimadzu GC/MS QP5050 or Jeol HX 100/110. PhI ¼ NTs was
prepared according to the reported procedure.25 Column chromatography
was performed on Merck silica gel 60 (230–400 mesh).
General experimental procedure: To a stirred suspension of Cu(OTf )2
(0.1 mmol), dry acetonitrile (5 mL) and PhI ¼ NTs (1.5 mmol) was added
allyl stannane (1 mmol) under dry nitrogen atmosphere. The resulting het-
erogeneous mixture was stirred for 2.5 h at room temperature. The reaction
mixture was filtered with silica gel pad. The filtrate was concentrated in
vacuum. The residue was purified by silica gel column chromatograpy to
give N-tosylallyl amines.
k
1
N-(Allyl-p-toluenesulfonamide (3a).7 H NMR (CDCl3) d7.70 (d,
J ¼ 8.3 Hz, 2H), 7.24 (d, J ¼ 8.3 Hz, 2H), 5.70–5.59 (m, 1H), 5.20–5.00
(m, 2H), 4.52 (br, 1H), 3.62–3.55 (m, 2H), 2.43 (s, 3H); 13C NMR (CDCl3)
d 143.5, 136.9, 132.9, 129.7, 127.1, 117.7, 45.8, 21.5; HRMS; calcd
for C10H13NO2S 211.0667, found 211.0674.

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KIM ET AL.
N-(Cyclopent-2-enyl)-p-toluenesulfonamide (3b). H NMR (CDCl3) d
1
7.75 (d, J ¼ 7.8 Hz, 2H), 7.35 (d, J ¼ 7.8 Hz, 2H), 5.30–5.71 (m, 2H), 4.39
(br, 1H), 3.50–3.62 (m, 1H), 2.43 (s, 3H), 2.40–2.20 (m, 2H), 2.20–1.95
(m, 2H); 13C NMR (CDCl3) d 134.2, 133.5, 130.9, 129.7, 127.1, 125.4, 45.4,
31.9, 29.7, 21.5; HRMS: calcd for C12H15NO2S 237.0824, found 237.0831.
N-(Cyclohex-2-enyl)-p-toluenesulfonamide (3c).1b 1H NMR (CDCl3) d
7.89 (d, J ¼ 8.1 Hz, 2H), 7.29 (d, J ¼ 8.1 Hz, 2H), 5.80–5.61 (m, 1H), 5.43–5.30
(m, 1H), 5.11 (br, 1H), 4.78 (br, 1H), 2.41 (s, 3H), 1.91–1.48 (m, 6H); 13C
NMR (CDCl3) d 143.2, 138.3, 131.2, 129.5, 127.0, 126.9, 48.9, 30.1, 24.4,
21.4, 19.3; HRMS: calcd for C13H17NO2S 251.0980, found 251.0975.
1
N-(Hex-2-enyl)-p-toluenesulfonamide (3d). H NMR (CDCl3) d 7.75
(d, J ¼ 8.1 Hz, 2H), 7.31 (d, J ¼ 8.1 Hz, 2H), 5.60–5.45 (m, 1H), 5.43–5.20
(m, 1H), 4.50 (br, 1H), 3.53 (t, J ¼ 6.3 Hz, 2H), 2.43 (s, 3H), 2.00–1.85 (m,
2H), 1.50–1.20 (m, 2H), 0.84 (t, J ¼ 7.2 Hz, 3H); 13C NMR (CDCl3) d 143.4,
137.8, 137.0, 134.5, 129.7, 129.4, 127.1, 124.4, 45.4, 37.6, 34.1, 22.0, 21.5,
13.6; HRMS: calcd for C13H19NO2S 253.1136, found 253.1130.
1
N-(1-Phenyl)allyl-p-toluenesulfonamide (3e). H NMR (CDCl3) d 7.63
(d, J ¼ 8.2 Hz, 2H), 7.40–7.05 (m, 7H), 5.98–5.80 (m, 1H), 5.20–5.05 (m, 2H),
4.94 (m, 1H), 4.76 (br, 1H), 2.39 (s, 3H), 13C NMR (CDCl3) d 142.6, 139.5,
137.6, 134.4, 129.7, 128.5, 127.1, 126.5, 124.6, 52.3, 21.4; HRMS: calcd for
C16H17NO2S 287.0980, found 287.0972
1
N-(3-Phenyl)allyl-p-toluenesulfonamide (3f ). H NMR (CDCl3) d 7.78
(d, J ¼ 8.1 Hz, 2H), 7.33–7.24 (m, 7H), 6.45 (d, J ¼ 16.0 Hz, 1H), 6.02 (dt,
J ¼ 16.0, 6.4 Hz, 1H), 4.50 (br, 1H), 3.76 (dt, J ¼ 6.4, 1.2 Hz, 2H), 2.43
(s, 3H); 13C NMR (CDCl3) d 143.6, 137.0, 136.0, 133.2, 129.8, 128.6,
128.0, 127.2, 126.4, 124.0, 45.5, 29.7; HRMS: calcd for C16H17NO2S
287.0980, found 287.0974.
ACKNOWLEDGMENT
This research was supported by research grants (No. 19990031) from
the Soonchunhyang University.
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Received in the USA November 10, 2000

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