Stereoselective synthesis of allylic amines by one-pot tandem reaction of acetylenic sulfone, Grignard reagent, and N-tosylimine

Article abstract of DOI:10.1080/00397910802226564

Polysubstituted allylic amines were regio- and stereoselectively synthesized by a one-pot tandem reaction of Cu(I)-catalyzed carbomagnesiation of acetylenic sulfones and its further reaction with N-tosylimine. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910802226564

This article was downloaded by: [University of South Carolina ]
On: 05 October 2014, At: 01:56
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Synthetic Communications: An
International Journal for Rapid
Communication of Synthetic
Organic Chemistry
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
Stereoselective Synthesis of
Allylic Amines by One-Pot
Tandem Reaction of Acetylenic
Sulfone, Grignard Reagent, and
N-Tosylimine
Mei-hua Xie a , Ying Sun a , Wei Zhang a , Xiao-xia Gu
a , Xin-yang Zhao a , Fa-dong Xie a & Shao-wu Wang a
a Anhui Key Laboratory of Functional Molecular
Solids, College of Chemistry and Materials Science,
Anhui Normal University , Wuhu, Anhui, China
Published online: 14 Oct 2008.
To cite this article: Mei-hua Xie , Ying Sun , Wei Zhang , Xiao-xia Gu , Xin-yang Zhao ,
Fa-dong Xie & Shao-wu Wang (2008) Stereoselective Synthesis of Allylic Amines by
One-Pot Tandem Reaction of Acetylenic Sulfone, Grignard Reagent, and N-Tosylimine,
Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 38:21, 3785-3796, DOI: 10.1080/00397910802226564
To link to this article: http://dx.doi.org/10.1080/00397910802226564
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,

or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Synthetic Communications1, 38: 3785–3796, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802226564
Stereoselective Synthesis of Allylic Amines by
One-Pot Tandem Reaction of Acetylenic Sulfone,
Grignard Reagent, and N-Tosylimine
Mei-hua Xie, Ying Sun, Wei Zhang, Xiao-xia Gu, Xin-yang Zhao,
Fa-dong Xie, and Shao-wu Wang
Anhui Key Laboratory of Functional Molecular Solids, College of
Chemistry and Materials Science, Anhui Normal University,
Wuhu, Anhui, China
Abstract: Polysubstituted allylic amines were regio- and stereoselectively synthe-
sized by a one-pot tandem reaction of Cu(I)-catalyzed carbomagnesiation of
acetylenic sulfones and its further reaction with N-tosylimine.
Keywords: Acetylenic sulfone, allylic amine, carbomagnesiation, Grignard
reagent, N-tosylimine
INTRODUCTION
Allylic amines are an important class of compounds in organic synthesis,
and they are used in the preparation of various synthetic intermediates.[1]
In addition, allylic amines are also common moieties in natural products
and pharmaceuticals.[2] Specific examples of the allylic amine-containing
drugs are flunarizine, naftifine, and terbinafine.[3] Because of their impor-
tance, there have been many literature reports for the preparation of
allylic amines, including (a) allylic amination catalyzed by the transition-
metal complexes, (b) hydroamination of allenes with amines,
(c) rearrangement of allylic sulfoximines, (d) allylation of imines, and
Received February 26, 2008.
Address correspondence to Mei-hua Xie, Anhui Key Laboratory of Func-
tional Molecular Solids, College of Chemistry and Materials Science, Anhui Nor-
mal University, Wuhu, Anhui241 000, China. E-mail: xiemh@mail.ahnu.edu.cn
3785

3786
M.-h. Xie et al.
(e) sigmatropic rearrangement of allylic ether derivatives.[4] However, it
appears that a simple, regio- and stereoselective synthetic route to allylic
amines of diverse substitution patterns is rare.[5]
Tetrasubstituted olefins are key structural elements of natural pro-
ducts and pharmaceutical such as terpenoids, nileprost, and tamoxifen.
Tetrasubstituted olefins are also important intermediates in organic
synthesis.[6] Carbometallation of alkynes is one of the most useful meth-
ods for olefin synthesis, because the resulting alkenylmetals can further
react with electrophiles to form various multisubstituted alkenes in a
stereoselective manner.[7] Vinyl sulfones are important precursors for
the synthesis of polysubstituted olefins because of the versatile reactivity
of sulfonyl and have remained an active research area for organic che-
mists.[8] Recently, we reported a regio- and stereoselective synthesis of
polysubstituted vinyl sulfone by the carbometallation of acetylenic sul-
fone followed by reaction with different electrophiles.[9] As an extension
of our research interest in regio- and stereoselective synthesis of polysub-
stituted olefins by carbometallation of acetylenic sulfone, we further
investigated the carbomagnesiation of acetylenic sulfone and its subse-
quent reaction with N-tosylimine. Herein, we report the synthesis of poly-
substituted allylic amines containing sulfone groups by one-pot tandem
reaction of acetylenic sulfone, Grignard reagent, and N-tosylimine.
RESULTS AND DISCUSSION
It has been reported that the reaction of Grignard reagent with acetylenic
sulfone afforded the products of overall substitution of the sulfone
moiety.[10] However, we found that the carbomagnesiation of acetylenic
sulfone proceeded smoothly in the presence of catalytic Cu(I).[9a]
Encouraged by the results, we examined the tandem reaction of phenyl-
magnesium bromide, acetylenic sulfone, and N-tosylimines in the
presence of Cu(I) for the synthesis of polysubstituted allylic amine
Scheme 1. Tandem reaction of acetylenic sulfone, phenylmagnesium bromide,
and N-tosylimine.

Stereoselective Synthesis of Allylic Amines
3787
Table 1. Reaction of acetylenic sulfone, Grignard reagent, and N-tosylimine
Entry
R1
R2
Product
Yield (%) (Z=E)a
1
2
3
4
5
6
7
8
9
C6H5–
C6H5–
C6H5–
C6H5–
C6H5–
C6H5–
C6H5–
C6H5–
C6H5–
C6H5–
3a
3b
3c
3d
3e
5a
5b
5c
5d
5e
5f
55
63
45
65
p-ClC6H4–
p-BrC6H4–
p-CH3OC6H4–
p-NO2C6H4–
C6H5–
p-ClC6H4–
p-BrC6H4–
p-CH3OC6H4–
C6H5–
10
90 (96=4)
70 (96=4)
52 (98=2)
95 (97=3)
40 (4=96)
42 (5=95)
52 (5=95)
10
11
12
n-C5H11–
n-C5H11–
n-C5H11–
p-ClC6H4–
p-BrC6H4–
5g
aIsolated yield based on the acetylenic sulfone used. The ratio of Z=E was determined by
300 MHz 1H NMR spectra of the unpurified reaction mixture.
(Scheme 1). At ꢀ20ꢁC, acetylenic sulfone was added to the solution of
phenylmagnesium bromide in tetrahydrofuran (THF)=CH2Cl2 in the
presence of 10 mol% CuCN. After the completion of the reaction, N-tosy-
limine was added. After stirring for another 8–12 h, the expected adducts
3 were obtained after purification. The results are summarized in Table 1
(entries 1–5, Table 1).
We further examined the similar tandem reaction of allylmagnesium
bromide, acetylenic sulfone, and N-tosylimines in the presence of
10 mol% Cu(I), hoping to introduce 1,4-diene structural unit into the tan-
dem reaction products (Scheme 2). The expected adducts 5 were obtained
by using the procedures similar to those used for synthesis of 3. The
results are summarized in Table 1 (entries 6–12, Table 1).
Table 1 shows that the a-sulfonyl vinyl magnesium bromide, which
is formed in situ from the Michael addition of Grignard reagent to
Scheme 2. Tandem reaction of acetylenic sulfone, allylmagnesium bromide, and
N-tosylimine.

3788
M.-h. Xie et al.
acetylenic sulfone, added to N-tosylimine gives the tandem reaction pro-
ducts with high stereoselectivity. The acetylenic sulfone can be phenyl-
(entries 1–9, Table 1) or alkyl-substituted (entries 10–12, Table 1)
acetylenic sulfone. The method is compatible with both electron-
withdrawing and electron-donating substituents on the aryl moiety of
the imines. However, the product 3e was obtained only in 10% yield when
the aryl of the imine is p-nitrophenyl (entry 5, Table 1). The Grignard
reagent can be phenylmagnesium bromide or allylmagnesium bromide.
When allylmagnesium bromide was used, the corresponding tetrasubsti-
tuted olefins containing allylic amine, and 1,4-diene structural units were
formed. Allylic amine and 1,4-diene[11] are important compounds in
organic synthesis. Therefore, it is predictable that the tetrasubstituted ole-
fins containing the structural units of allylic amine and 1,4-diene can be
useful intermediates in organic synthesis.
The stereochemistry of the tandem reaction was verified by the X-ray
structure of compound 5a (Fig. 1). From Fig. 1, we can see that the
phenyl attached to C(29) is cis oriented with the tosyl attached to
C(28) and the allyl is trans oriented with the tosyl attached to C(28).
The result suggests that the tandem reaction of acetylenic sulfone, allyl-
magnesium bromide, and N-tosylimine is in the syn-fashion. The similar-
ity of the 1H NMR signals of the benzyl proton, which show a doublet at
d ¼ 6.25–5.91 ppm with a coupling constant of 10.2–10.4 Hz, indicates
that compounds 5a–g were formed in the same stereochemistry.
In conclusion, we have developed a regio- and stereoselective
method for the preparation of polysubstituted allylic amines by the tandem
reaction of acetylenic sulfone, Grignard reagent, and N-tosylimine. The
Figure 1. Molecular structure of compound 5a.

Stereoselective Synthesis of Allylic Amines
3789
presence of the sulfonyl in products offers potential for further synthetic
transformations. The method has the advantages of convenient manipula-
tion, easily available starting materials, and high regio- and stereoselectivity.
EXPERIMENTAL
All the solid products were recrystallized from ethyl acetate and hexane,
and the melting points are uncorrected. All manipulations were performed
under an oxygen-free atmosphere of argon with rigid exclusion of moisture
from reagents and glassware unless otherwise noted. THF and Et2O were
distilled from sodium=benzophenone. CH2Cl2 was distilled from calcium
1
hydride, H NMR spectra were measured at 300 MHz, and 13C NMR
spectra were measured at 75 MHz in CDCl3 with TMS as the internal stan-
dard on a Bruker AV 300 spectrometer. MS (EI, 70 eV) were determined
on a CA 064 mass spectrometer. High resolution mass spectra (HRMS)
[electrospray ionization (ESI)] was determined on a Bruker Fourier trans-
form-ion cyclotron resonance mass spectrometer (FT-ICRMS). IR spectra
were recorded as KBr disks on a Fourier transform-infrared (FT-IR)-8400
spectrometer. Acetylenic sulfones[12] and N-tosylimines[13] were prepared
according to previously described procedures.
General Procedure for the Preparation of Polysubstituted Allylic
Amines 3a–e
To a solution of phenylmagnesium bromide (0.75 mmol) in THF=CH2Cl2
(v=v ¼ 1=4, 5 mL) were added CuCN (10 mol%) and 1-phenyl-2-(p-
tosyl)ethyne (0.5 mmol) at ꢀ20ꢁC with stirring. After carbomagnesiation
of the acetylenic sulfone was complete (monitored by thin-layer chroma-
tography, TLC), N-tosylimine (0.75 mmol) was added at ꢀ20ꢁC. The
reaction mixture was stirred for another 8–12 h at room temperature,
quenched with saturated NH4Cl, and extracted with CH2Cl2. The organic
phase was dried over Na2SO4. After filtration and removal of solvent in
vacuo, the crude product was purified with flash chromatography (silica=
hexanes–ethyl acetate 8:1 v=v). The desired products 3 were obtained.
Data
4-Methyl-N-(1,3,3-triphenyl-2-tosylallyl)benzenesulfonamide (3a)
1
White solid, mp 165–167 ꢁC. H NMR (300 MHz, CDCl3): d ¼ 7.58 (d,
J ¼ 8.1 Hz, 2H), 7.30–7.14 (m, 13H), 7.07–6.90 (m, 7H), 6.79 (d,

3790
M.-h. Xie et al.
J ¼ 7.1 Hz, 2H) 5.89 (d, J ¼ 10.5 Hz, 1H), 2.40 (s, 3H), 2.33 (s, 3H). 13C
NMR (75 MHz, CDCl3): d ¼ 154.8, 144.2, 143.4, 143.3, 142.4, 139.5,
138.5, 138.1, 137.9, 131.3, 129.4, 129.0, 128.9, 128.8, 128.7, 128.4,
127.9, 127.6, 127.3, 126.6, 123.6, 120.8, 58.3, 21.5. IR (KBr): 3327,
1597, 1492, 1337, 1155 cmꢀ1. MS (EI): m=z (%) ¼ 438 (30, M–Ts), 283
(8), 267 (100), 178 (74), 91 (54). HRMS calcd. for C35H31NNaO4S2
(MNaþ): 616.1592; found: 616.1564.
N-(1-(4-Chlorophenyl)-3,3-diphenyl-2-tosylallyl)-4-methylbenzenesulfo-
namide (3b)
1
White solid, mp 234–235 ꢁC. H NMR (300MHz, CDCl3): d ¼ 7.55 (d,
J ¼ 8.4 Hz, 2H), 7.34ꢀ7.32 (m, 3H), 7.25–7.14 (m, 9H), 7.07–6.92 (m,
7H), 6.76 (d, J ¼ 6.9 Hz, 2H), 5.86 (d, J ¼ 10.5 Hz, 1H), 2.41 (s, 3H), 2.34
(s, 3H). 13C NMR (75 MHz, CDCl3): d ¼ 155.1, 143.6, 143.5, 141.9, 139.4,
138.2, 137.7, 136.6, 133.5, 129.5, 129.1, 129.0, 128.9, 128.8, 128.5, 128.1,
127.9, 127.6, 127.5, 127.2, 58.0, 21.5. IR (KBr): 3381, 1595, 1491, 1344,
1140cmꢀ1. MS (EI): m=z (%) ¼ 472 (40, M–Ts), 474 (16, M–Ts), 301 (68),
303 (23), 178 (100), 91 (85). Anal. calcd. for C35H30ClNO4S2: C, 66.92; H,
4.81; N, 2.23; found: C, 66.96; H, 5.00; N, 2.10.
N-(1-(4-Bromophenyl)-3,3-diphenyl-2-tosylallyl)-4-methylbenzenesulfo-
namide (3c)
1
White solid, mp 125–127 ꢁC. H NMR (300 MHz, CDCl3): d ¼ 7.58 (d,
J ¼ 7.7 Hz, 2H), 7.39–7.30 (m, 5H), 7.22–7.17 (m, 7H), 7.10–7.05 (m,
4H), 7.01–6.96 (m, 3H), 6.80 (d, J ¼ 7.1 Hz, 2H), 5.87 (d, J ¼ 10.5 Hz,
1H), 2.44 (s, 3H), 2.36 (s, 3H). 13C NMR (75 MHz, CDCl3): d ¼ 154.9,
143.3, 143.2, 141.5, 139.0, 137.8, 136.8, 131.1, 129.4, 129.1, 128.8,
128.7, 128.6, 128.5, 128.1, 127.7, 127.6, 127.3, 127.1, 126.8, 126.1,
121.3, 57.7, 21.2. IR (KBr): 3377, 1595, 1491, 1342, 1140 cmꢀ1. MS
(EI): m=z (%) ¼ 516 (16, M–Ts), 518 (17, M–Ts), 346 (9), 348 (9), 178
(100), 91 (54). Anal. calcd. for C35H30BrNO4S2: C, 62.50; H, 4.50; N,
2.08; found: C, 62.58; H, 4.52; N, 2.01.
N-(1-(4-Methoxyphenyl)-3,3-diphenyl-2-tosylallyl)-4-methylbenzenesul-
fonamide (3d)
1
White solid, mp 200–202 ꢁC. H NMR (300 MHz, CDCl3): d ¼ 7.59 (d,
J ¼ 8.1 Hz, 2H), 7.33–7.29 (m, 3H), 7.23–7.16 (m, 7H), 7.10–7.06 (m,
4H), 7.04–6.91 (m, 3H), 6.79 (d, J ¼ 8.4 Hz, 4H), 5.86 (d, J ¼ 10.5 Hz,

Stereoselective Synthesis of Allylic Amines
3791
1H), 3.81 (s, 3H), 2.42 (s, 3H), 2.36 (s, 3H). 13C NMR (75 MHz, CDCl3):
d ¼ 158.9, 154.4, 143.4, 143.2, 142.4, 139.5, 138.5, 138.0, 130.1, 129.4,
129.1, 128.9, 128.7, 128.0, 127.9, 127.6, 127.5, 127.2, 113.7, 58.0, 55.6,
21.5. IR (KBr): 3365, 1595, 1442, 1339, 1140 cmꢀ1. MS (EI): m=z
(%) ¼ 468 (42, M - Ts), 298 (34), 178 (100), 91 (83). HRMS calcd. for
C36H33NNaO5S2 (MNaþ), 646.1698; found: 646.1692.
4-Methyl-N-(1-(4-nitrophenyl)-3,3-diphenyl-2-tosylallyl)benzenesulfona-
mide (3e)
1
White solid, mp 281–283 ꢁC. H NMR (300 MHz, CDCl3): d ¼ 8.1 (d,
J ¼ 8.4 Hz, 2H), 7.57 (d, J ¼ 7.9 Hz, 2H), 7.44 (d, J ¼ 8.5 Hz, 2H), 7.37–
7.34 (m, 3H), 7.21–7.17 (m, 5H), 7.09–6.97 (m, 7H), 6.77 (d, J ¼ 6.9 Hz,
2H), 6.01 (d, J ¼ 10.2 Hz, 1H), 2.41 (s, 3H), 2.34 (s, 3H). 13C NMR
(75 MHz, CDCl3): d ¼ 156.3, 156.1, 149.6, 147.2, 145.8, 143.8, 142.1,
139.1, 138.2, 137.6, 130.5, 129.6, 129.4, 129.0, 128.3, 128.0, 127.7,
127.4, 127.1, 123.5, 28.2, 21.5. IR (KBr): 3358, 1595, 1517, 1441, 1480,
1342, 1339, 1142 cmꢀ1. MS (EI): m=z (%) ¼ 483 (100, M–Ts), 313 (14),
178 (49), 91 (52). Anal. calcd. for C35H30N2O6S2: C, 65.81; H, 4.73; N,
4.39; found: C, 65.78; H, 4.76; N, 4.42.
General Procedure for the Preparation of Polysubstituted Allylic Amines
5a–g
CuCN (10mol%) and acetylenic sulfone (0.5mmol) were added to a solution
of allylmagnesium bromide (0.75 mmol) in Et2O=CH2Cl2 (v=v¼ 1=4, 5 mL)
at ꢀ20ꢁC with stirring. After carbomagnesiation of the acetylenic sulfone
was complete (monitored by TLC), N-tosylimine (0.75 mmol) was added
at ꢀ 20ꢁC. The reaction mixture was stirred for another 8–12 h at room tem-
perature, quenched with saturated NH4Cl, and extracted with CH2Cl2. The
organic phase was dried over Na2SO4. After filtration and removal of solvent
in vacuo, the crude product was purified with flash chromatography (silica=
hexanes–ethyl acetate 8:1 v=v). The desired products 5 were obtained.
Data
(Z)-N-(1,3-Diphenyl-2-tosyl-2,5-hexadienyl)-4-methylbenzenesulfona-
mide (5a)
1
White solid, mp 140–143 ꢁC. H NMR (300 MHz, CDCl3): d ¼ 7.90 (d,
J ¼ 8.1 Hz, 2H), 7.44–7.28 (m, 8H), 7.19–7.17 (m, 2H), 7.09–7.01 (m,

3792
M.-h. Xie et al.
2H), 6.86–6.83 (m, 3H), 6.72 (d, J ¼ 8.2 Hz, 2H), 6.25 (d, J ¼ 10.3 Hz,
1H), 5.62–5.47 (m, 1H), 5.03–4.98 (m, 2H), 3.68–3.61 (m, 1H), 3.14–
3.08 (m, 1H), 2.48 (s, 3H), 2.30 (s, 3H). 13C NMR (75 MHz, CDCl3):
d ¼ 153.0, 143.2, 142.8, 141.3, 138.1, 138.0, 137.6, 136.9, 131.4, 129.4,
129.2, 128.3, 128.2, 128.1, 127.5, 127.3, 127.1, 127.0, 126.9, 126.0,
118.5, 55.8, 42.6, 21.2, 21.1. IR (KBr): 3358, 1595, 1441, 1335,
1136 cmꢀ1. MS (EI): m=z (%) ¼ 402 (38, M–Ts), 232 (22), 231 (100), 91
(45). Anal. calcd. for C32H31NO4S2: C, 68.91; H, 5.60; N, 2.51; found:
C, 68.86; H, 5.62; N, 2.53.
(Z)-N-(1-(4-Chlorophenyl)-3-phenyl-2-tosyl-2,5-hexadienyl)-4-methyl-
benzenesulfonamide (5b)
1
White solid, mp 163–165 ꢁC. H NMR (300 MHz, CDCl3) d 7.88 (d,
J ¼ 8.8 Hz, 2H), 7.35–7.26 (m, 7H), 7.21–7.19 (m, 2H), 7.08 (m, 2H),
6.90–6.79 (m, 5H), 6.20 (d, J ¼ 10.2 Hz, 1H), 5.60–5.49 (m, 1H), 5.07–
5.02 (m, 2H), 3.72–3.67 (m, 1H), 3.10–3.06 (m, 1H), 2.50 (s, 3H), 2.32 (s,
3H). 13C NMR (75 MHz, CDCl3): d ¼ 153.2, 143.4, 142.9, 141.1, 137.9,
137.8, 136.9, 136.2, 133.2, 131.4, 129.4, 129.1, 128.8, 128.3, 127.6, 127.4,
127.2, 126.9, 126.8, 118.6, 55.3, 42.6, 21.2, 21.1. IR (KBr): 3352, 1597,
1443, 1344, 1138 cmꢀ1. MS (EI): m=z (%) ¼ 436 (55, M–Ts), 438 (21),
226 (35), 265 (100), 171 (10). Anal. calcd. for C32H30ClNO4S2: C, 64.90;
H, 5.11; N, 2.37; found: C, 64.67; H, 5.16; N, 2.35.
(Z)-N-(1-(4-Bromophenyl)-3-phenyl-2-tosyl-2,5-hexadienyl)-4-methyl-
benzenesulfonamide (5c)
1
White solid, mp 155–157 ꢁC. H NMR (300 MHz, CDCl3): d ¼ 7.87 (d,
J ¼ 8.1 Hz, 2H), 7.53–7.07 (m, 9H), 6.89–6.77 (m, 7H), 6.17 (d, J ¼ 10.2 Hz,
1H), 5.61–5.47 (m, 1H), 5.05–5.00 (m, 2H), 3.72–3.65 (m, 1H), 3.10–3.04
(m, 1H), 2.45 (s, 3H), 2.31 (s, 3H). 13C NMR (75 MHz, CDCl3):
d ¼ 153.3, 143.4, 143.0, 141.0, 137.9, 137.8, 136.8, 136.6, 132.0, 131.4,
131.2, 129.2, 128.4, 127.7, 127.6, 127.2, 126.9, 126.8, 121.3, 118.6, 55.4,
42.6, 21.2, 21.1. IR (KBr): 3352, 1595, 1485, 1443, 1342, 1138 cmꢀ1. MS
(EI): m=z (%) ¼ 480 (30, MꢀTs), 482 (31), 310 (27), 91 (100). HRMS
calcd. for C32H30BrNNaO4S2 (MNaþ), 658.0697; found: 658.0692.
(Z)-N-(1-(4-Methoxyphenyl)-3-phenyl-2-tosyl-2,5-hexadienyl)-4-methyl-
benzenesulfonamide (5d)
White solid, mp 72–75 ꢁC. 1H NMR (300 MHz, CDCl3): d ¼ 7.89 (d,
J ¼ 8.1 Hz, 2H), 7.36–7.27 (m, 7H), 7.18–7.16 (m, 2H), 7.12–6.98 (m,

Stereoselective Synthesis of Allylic Amines
3793
2H), 6.88–6.75 (m, 5H), 6.19 (d, J ¼ 10.4 Hz, 1H), 5.59–5.44 (m, 1H),
5.03–4.97 (m, 2H), 3.82 (s, 3H), 3.68–3.61 (m, 1H), 3.12–3.05 (m, 1H),
2.48 (s, 3H), 2.30 (s, 3H). 13C NMR (75 MHz, CDCl3): d ¼ 158.7,
152.6, 143.1, 142.8, 141.3, 138.1, 137.0, 131.5, 129.4, 129.2, 128.3,
128.0, 127.5, 127.1, 127.0, 126.9, 126.7, 118.5, 113.5, 113.4, 55.4, 55.0,
42.5, 21.2, 21.1. IR (KBr): 3368, 1597, 1422, 1337, 1140 cmꢀ1. MS (EI):
m=z (%) ¼ 432 (46, MꢀTs), 277 (10), 261 (100), 91 (38). Anal. calcd. for
C33H33NO5S2: C, 67.44; H, 5.66; N, 2.38; found: C, 67.56; H, 5.58; N,
2.35.
(E)-N-(3-Allyl-1-phenyl-2-tosyl-2-octenyl)-4-methylbenzene-
sulfonamide (5e)
1
White solid, mp 98–100 ꢁC. H NMR (300 MHz, CDCl3): d ¼ 7.76 (d,
J ¼ 8.1 Hz, 2H), 7.36–7.26 (m, 4H), 7.15–7.01 (m, 7H), 6.63 (d, J ¼ 9.6 Hz,
1H), 6.01 (d, J ¼ 10.2 Hz, 1H), 5.75–5.55 (m, 1H), 5.13–5.08 (m, 2H),
3.30–3.28 (m, 1H), 2.91–2.87 (m, 1H), 2.56–2.49 (m, 1H), 2.42 (s, 3H),
2.37 (s, 3H), 2.19–2.11 (m, 1H), 1.25–0.93 (m, 6H), 0.83 (t, J ¼ 6.3 Hz,
3H). 13C NMR (75 MHz, CDCl3): d ¼ 156.7, 143.6, 143.2, 139.5, 138.2,
138.0, 136.4, 132.9, 132.5, 129.4, 129.1, 128.9, 128.0, 127.5, 126.5,
126.1, 118.6, 55.0, 38.4, 33.8, 31.8, 26.9, 22.1, 21.2, 13.6. IR (KBr):
3306, 1597, 1468, 1337, 1137 cmꢀ1. MS (EI): m=z (%) ¼ 396 (42, MꢀTs),
248 (100), 91 (53). Anal. calcd. for C31H37NO4S2: C, 67.48; H, 6.76; N,
2.54; found: C, 67.65; H, 6.58; N, 2.61.
(E)-N-(3-Allyl-1-(4-chlorophenyl)-2-tosyl-2-octenyl)-4-methylbenzene-
sulfonamide (5f)
White solid, mp 100–102 ꢁC. 1H NMR (300 MHz, CDCl3): d ¼ 7.67
(d, J ¼ 8.1 Hz, 2H), 7.40–7.16 (m, 4H), 7.06–6.97 (m, 6H), 6.48
(d, J ¼ 11.0 Hz, 1H), 5.91 (d, J ¼ 10.2 Hz, 1H), 5.70–5.51 (m, 1H),
5.04–5.00 (m, 2H), 3.30–3.21 (m, 1H), 2.81–2.75 (m, 1H), 2.52–2.48
(m, 1H), 2.47 (s, 3H), 2.36 (s, 3H), 2.09–2.05 (m, 1H), 1.29–1.16
(m, 6H), 0.78 (t, J ¼ 6.3 Hz, 3H). 13C NMR (75 MHz, CDCl3):
d ¼ 156.7, 143.6, 143.2, 139.5, 138.2, 138.0, 136.3, 132.9, 132.5, 129.8,
129.4, 128.6, 128.0, 126.8, 126.5, 118.6, 55.0, 38.4, 33.9, 31.8, 26.9,
22.1, 21.2, 13.6. IR (KBr): 3305, 1613, 1490, 1338, 1140 cmꢀ1. MS (EI):
m=z (%) ¼ 430 (100, MꢀTs), 432 (37), 259 (31), 91 (96). Anal. calcd. for
C31H36ClNO4S2: C, 63.52; H, 6.19; N, 2.39; found: C, 63.80; H, 6.25;
N, 2.50.

3794
M.-h. Xie et al.
(E)-N-(3-Allyl-1-(4-bromophenyl)-2-tosyloct-2-enyl)-4-methylbenzene-
sulfonamide (5g)
1
White solid, mp 120–123 ꢁC. H NMR (300 MHz, CDCl3): d 7.76 (d,
J ¼ 8.1 Hz, 2H), 7.35–7.27 (m, 6H), 7.15–7.02 (m, 4H), 6.62 (d,
J ¼ 10.2 Hz, 1H), 5.98 (d, J ¼ 10.2 Hz, 1H), 5.71–5.63 (m, 1H), 5.14–
5.08 (m, 2H), 3.33–3.31 (m, 1H), 2.89–2.86 (m, 1H), 2.59–2.45 (m, 1H),
2.43 (s, 3H), 2.38 (s, 3H), 2.18–2.15 (m, 1H), 1.40–1.10 (m, 6H), 0.83
(t, J ¼ 6.6 Hz, 3H). 13C NMR (75 MHz, CDCl3): d ¼ 156.8, 143.6,
143.2, 139.5, 138.1, 138.0, 136.9, 132.6, 130.9, 129.4, 129.1, 127.9,
126.5, 121.1, 118.6, 55.1, 38.4, 33.9, 31.8, 27.0, 22.1, 21.2, 13.6. IR
(KBr): 3302, 1597, 1487, 1337, 1136 cmꢀ1. MS (EI): m=z (%) ¼ 474 (57,
MꢀTs), 476 (57), 304 (37), 303 (73), 91 (100). HRMS calcd. for
C31H36BrNNaO4S2 (MNaþ), 652.1167; found: 652.1161.
Crystal Data for 5a
C32H31NO4S2, MW ¼ 557.70, monoclinic, space group P2(1)=n,
a ¼ 11.3881(2), b ¼ 15.2974(2), c ¼ 17.1238(3) A; a ¼ 90ꢁ, b ¼
˚
3
ꢁ
ꢁ
˚
˚
107.6200(10) , c ¼ 90 . V ¼ 2843.16(8) A , T ¼ 293 K, Z ¼ 4, Dc ¼
1.303 g cmꢀ1, m ¼ 0.225 mm , k ¼ 0.71073 A; F(000) 1176, 4975 indepen-
–1
dent reflections (Rint ¼ 0.1229), 13455 reflections collected; refinement
method, Full-matrix least-squares on F2; goodness-of-fit on F2 ¼ 1.055;
final R indices [I > 2r(I)] R1 ¼ 0.0374, wR2 ¼ 0.0975.
ACKNOWLEDGMENTS
The authors are grateful to the National Natural Science Foundation of
China (No. 20672001 and 20772001) and the Anhui Education Depart-
ment (No. TD200707) for financial support of this research. We are also
grateful to Jiping Hu, Gaosheng Yang, Baohui Du, and Yun Wei for
their helpful assistance.
REFERENCES
1. (a) Nishina, N.; Yamamoto, Y. Gold-catalyzed intermolecular hydroamina-
tion of allenes with arylamines and resulting high chirality transfer. Angew.
ꢀ
Chem. Int. Ed. 2006, 45, 3314–3317; (b) Garcıa-Egido, E.; Fernandez, I.;
Munoz, L. Convenient synthesis of oxazolidinones and oxazinones from allyl
´
~
and homoallyl amines under mild conditions. Synth. Commun. 2006, 36,

Stereoselective Synthesis of Allylic Amines
3795
3029–3042; (c) Hodgson, D. M.; Fleming, M. J.; Stanway, S. J. One-carbon
homologation of N-sulfonylaziridines to allylic amines using dimethylsulfo-
nium methylide. Org. Lett. 2005, 7, 3295–3298; (d) Ichikawa, Y.; Ito, T.;
Nishiyama, T.; Isobe, M. Stereoselective allyl amine synthesis via enantiose-
lective addition of diethylzinc and sigmatropic rearrangement: Synthesis of
lentiginosine. Synlett 2003, 1034–1036; (e) Johannsen, M.; Jørgensen, K. A.
Allylic Amination. Chem. Rev. 1998, 98, 1689–1708.
2. (a) Matsui, K.; Takizawa, S.; Sasai, H. Bifunctional organocatalysts for enan-
tioselective aza-morita-baylis-hillman reaction. J. Am. Chem. Soc. 2005, 127,
3680–3681; (b) Katritzky, A. R.; Yao, J. C.; Qi, M. Palladium-catalyzed reac-
tion of N-allylbenzotriazoles with amines: A novel method for the prepara-
tion of allylamines. J. Org. Chem. 1998, 63, 5232–5234; (c) Kondo, T.;
Nakai, H.; Goto, T. Synthesis of cytosinine, the nucleoside component of
antibiotic blasticidin S. Tetrahedron 1973, 29, 1801–1806.
3. Chen, G.; Sasaki, M.; Yudin, A. K. Facile preparation of allyl amines and
pyrazoles by hydrazinolysis of 2-ketoaziridines. Tetrahedron Lett. 2006, 47,
255–259 and references therein.
ꢀ
ꢀ
4. (a) Concellon, J. M.; Suarez, J. R.; Solar, V. Synthesis of enantiopure allyla-
mines by reductive alkylation of amino epoxides with organolithium reagents.
Org. Lett. 2006, 8, 349–351; (b) Singh, V.; Pathak, R.; Kanojiya, S.; Batra, S.
A reinvestigation into the reaction of NH4OAc with acetyl derivatives of
baylis-hillman adducts: Formation of tertiary and secondary allyl amines
instead of primary allyl amines. Synlett 2005, 2465–2468; (c) Yamasaki, S.;
Fujii, K.; Wada, R.; Kanai, M.; Shibasaki, M. A General catalytic allylation
using allyltrimethoxysilane. J. Am. Chem. Soc. 2002, 124, 6536–6537; (d)
Evans, P. A.; Robinson, J. E.; Nelson, J. D. Enantiospecific synthesis of ally-
lamines via the regioselective rhodium-catalyzed allylic amination reaction. J.
Am. Chem. Soc. 1999, 121, 6761–6762; (e) Marson, C. M.; Hobson, A. D. In
Comprehensive Organic Functional Group Transformations; A. R. Katrizky,
O. Meth-Cohn, C. W. Rees (Eds.); Pergamon: Oxford, 1995, vol. 2, p. 297.
5. (a) Back, T. G.; Rankic, D. A.; Sorbetti, J. M.; Wulff, J. E. Morita-baylis-
hillman reaction and cyclization of 1-(p-toluenesulfonyl)-1,3-butadiene with
aldimines. Org. Lett. 2005, 7, 2377–2379; (b) Dieter, R. K.; Dieter, J. W.;
Alexander, C. W.; Bhinderwala, N. S. Efficient synthesis of allylic amines
from a-aminoalkyl cuprates and enol triflates. J. Org. Chem. 1996, 61,
2930–2931.
6. (a) Zhou, C. X.; Larock, R. C. Regio- and stereoselective route to tetrasubsti-
tuted olefins by the palladium-catalyzed three-component coupling of aryl
iodides, internal alkynes, and arylboronic acids. J. Org. Chem. 2005, 70,
3765–3777; (b) Itami, K.; Mineno, M.; Muraoka, N.; Yoshida, J. Sequential
assembly strategy for tetrasubstituted olefin synthesis using vinyl 2-pyrimidyl
sulfide as a platform. J. Am. Chem. Soc. 2004, 126, 11778–11779; (c)
Studemann, T.; Knochel, P. New nickel-catalyzed carbozincation of alkynes:
¨
A short synthesis of (Z)-tamoxifen. Angew. Chem., Int. Ed. Engl. 1997, 36, 93–95.
7. (a) Shirakawa, E.; Yamagami, T.; Kimura, T.; Yamaguchi, S.; Hayashi, T.
Arylmagnesiation of alkynes catalyzed cooperatively by iron and copper

3796
M.-h. Xie et al.
complexes. J. Am. Chem. Soc. 2005, 127, 17164–17165; (b) Maezaki, N.;
Sawamoto, H.; Suzuki, T.; Yoshigami, R.; Tanaka, T. Highly stereoselective
synthesis of functionalized b,b-di- and trisubstituted vinylic sulfoxides by
Cu-catalyzed conjugate addition of organozinc reagents. J. Org. Chem.
2004, 69, 8387–8393.
8. (a) Simpkins, N. S. Sulfones in Organic Synthesis; Pergamon Press: Oxford,
ꢀ
UK, 1993; (b) Ba¨ckvall, J. E.; Chinchilla, R.; Najera, C.; Yus, M. The use
of sulfonyl 1,3-dienes in organic synthesis. Chem. Rev. 1998, 98, 2291–2312.
9. (a) Xie, M. H.; Wang, J. L.; Gu, X. X.; Sun, Y.; Wang, S. W. Highly
regio- and stereoselective synthesis of tetrasubstituted olefins by the three-
component tandem reaction of allylzinc bromide, acetylenic sulfone, and
halohydrocarbon. Org. Lett. 2006, 8, 431–434; (b) Xie, M. H.; Huang, X.
Carbomagnesiation of acetylenic sulfones catalyzed by CuCN and its applica-
tion in the stereoselective synthesis of polysubstituted vinyl sulfones. Synlett
2003, 477–480.
10. Smorada, R. L.; Truce, W. E. Reactions of arylsulfonylacetylenes with orga-
nolithium and grignard reagents: A new synthesis of acetylenes. J. Org.
Chem. 1979, 44, 3444–3445.
11. (a) Hadani, A. N.; Rawal, V. H. Stereospecific synthesis of highly substituted
skipped dienes through multifunctional palladium catalysis. Org. Lett. 2002,
4, 4317–4320; (b) Okamoto, S.; Takayama, Y.; Gao, Y.; Sato, F. One-pot
synthesis of a variety of 1,4-alkadienes and 1,2,4-alkatrienes from alkynes,
allyl, or propargyl compounds and electrophiles by a (g2-propene)Ti(O-i-
Pr)2-mediated reaction. Synthesis 2000, 975–979.
12. Truce, W. E.; Wolf, G. C. Adducts of sulfonyl iodides with acetylenes. J. Org.
Chem. 1971, 36, 1727–1732.
13. Love, B. E.; Raje, P. S.; Williams, T. C. Preparation of N-tosylaldimines.
Synlett 1994, 493–494.