Unprecedented CO2-promoted aminochlorination of olefins with Chloramine-T

Article abstract of DOI:10.1021/ol0600178

A new synthetic procedure for the aminochlorination of olefins for the synthesis of vicinal chloroamine derivatives using a combination of Chloramine-T and carbon dioxide is described. The method can be applied to a variety of olefins, including an electr

Full text of DOI:10.1021/ol0600178

ORGANIC
LETTERS
2
006
Vol. 8, No. 5
67-969
Unprecedented CO -Promoted
Aminochlorination of Olefins with
Chloramine-T
2
9
Satoshi Minakata,*,† Yoshimi Yoneda, Yoji Oderaotoshi, and
†
†
Mitsuo Komatsu*,
†,‡,§
Department of Applied Chemistry, Center for Atomic and Molecular Technologies,
Graduate School of Engineering, Osaka UniVersity, Yamadaoka 2-1, Suita,
Osaka 565-0871, Japan, and Research Center for EnVironmental PreserVation,
Osaka UniVersity, Yamadaoka 2-4, Suita, Osaka 565-0871, Japan
komatsu@chem.eng.osaka-u.ac.jp
Received January 3, 2006
ABSTRACT
A new synthetic procedure for the aminochlorination of olefins for the synthesis of vicinal chloroamine derivatives using a combination of
Chloramine-T and carbon dioxide is described. The method can be applied to a variety of olefins, including an electron-sufficient olefin and
a conjugated diene.
a combination of a sulfonamide and NBS. In our6
a-f
Vicinal haloamine derivatives are versatile synthetic inter-
mediates for the synthesis of functional materials and
biologically active compounds. Among the synthetic routes
continuing efforts to provide new methods for synthesis of
1
to these 1,2-haloamines, the direct 1,2-functionalization of
olefins is a practical method, due to the fact that the starting
materials are readily available olefins. Although noncatalytic
procedures for the preparation of 1,2-haloamines by the
addition of N-halo derivatives to olefins have been reported,
(3) (a) Li, G.; Wei, H.-X.; Kim, S. H.; Neighbors, M. Org. Lett. 1999,
1
2
, 395-397. (b) Li, G.; Wei, H.-X.; Kim, S. H. Org. Lett. 2000, 2, 2249-
252. (c) Wei, H.-X.; Kim, S. H.; Li, G. Tetrahedron 2001, 57, 3869-
3873. (d) Wei, H.-X.; Kim, S. H.; Li, G. Tetrahedron 2001, 57, 8407-
8
2
411. (e) Chen, D.; Timmons, C.; Chao, S.; Li, G. Eur. J. Org. Chem.
004, 3097-3101. (f) Kotti, S. R. S. S.; Xu, X.; Wang, Y.; Headley, A.
D.; Li, G. Tetrahedron Lett. 2004, 45, 7209-7212. (g) Xu, X.; Kotti, S. R.
S. S.; Liu, J.; Cannon, J. F.; Headley, A. D.; Li, G. Org. Lett. 2004, 6,
4881-4884. (h) Chen, D.; Guo, L.; Liu, J.; Kirtane, S.; Cannon, J. F.; Li,
G. Org. Lett. 2005, 7, 921-924.
2
these processes suffer from low efficiency.
3
4
5
Li and Sudalai and other groups recently reported on
the elegant aminohalogenation of olefins catalyzed by
transition metal salts using an N,N-dichlorosulfonamide or
(4) Thakur, V. V.; Talluri, S. K.; Sudalai, A. Org. Lett. 2003, 5, 861-
8
64.
(5) (a) SÄ liwi n´ ska, A.; Zwierzak, A. Tetrahedron 2003, 59, 5927-5934.
(
b) Qi, X.; Lee, S.-H.; Kwon, J. Y.; Kim, Y.; Kim, S.-J.; Lee, Y.-S.; Yoon,
†
Department of Applied Chemistry.
Center for Atomic and Molecular Technologies.
Research Center for Environmental Preservation.
J. J. Org. Chem. 2003, 68, 9140-9143. (c) Manzoni, M. R.; Zabawa, T.
P.; Kasi, D.; Chemler, S. R. Organometallics 2004, 23, 5618-5621.
(6) (a) Ando, T.; Minakata, S.; Ryu, I.; Komatsu, M. Tetrahedron Lett.
1998, 39, 309-312. (b) Ando, T.; Kano, D.; Minakata, S.; Ryu, I.; Komatsu,
M. Tetrahedron 1998, 54, 13485-13494. (c) Kano, D.; Minakata, S.;
Komatsu, M. J. Chem. Soc., Perkin Trans. 1 2001, 3186-3188. (d)
Minakata, S.; Kano, D.; Oderaotoshi, Y.; Komatsu, M. Org. Lett. 2002, 4,
2097-2099. (e) Minakata, S.; Kano, D.; Fukuoka, R.; Oderaotoshi, Y.;
Komatsu, M. Heterocycles 2003, 60, 289-298. (f) Minakata, S.; Kano,
D.; Oderaotoshi, Y.; Komatsu, M. Angew. Chem., Int. Ed. 2004, 43, 79-
81. Sharpless’s group also found a elegant method. See: (g) Jeong, J. U.;
Tao, B.; Sagasser, I.; Henniges, H.; Sharpless, K. B. J. Am. Chem. Soc.
1998, 120, 6844-6845.
‡
§
(
1) Kemp, J. E. G. In ComprehensiVe Organic Synthesis; Trost, B. M.,
Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 7, pp 469-513.
2) (a) Kharasch, M. S.; Priestley, H. M. J. Am. Chem. Soc. 1939, 61,
425-3432. (b) Ueno, Y.; Takemura, S.; Ando, Y.; Terauchi, H. Chem.
(
3
Pharm. Bull. 1967, 15, 1193-1197. (c) Daniher, F. A.; Butler, P. E. J.
Org. Chem. 1968, 33, 4336-4340. (d) Terauchi, H.; Takemura, S.; Ueno,
Y. Chem. Pharm. Bull. 1975, 23, 640-645. (e) Zawadzki, S.; Zwierzak,
A. Tetrahedron 1981, 37, 2675-2681. (f) Klepacz, A.; Zwierzak, A.
Tetrahedron Lett. 2001, 42, 4539-4540. (g) Tsuritani, T.; Shinokubo, H.;
Oshima, K. J. Org. Chem. 2003, 68, 3246-3250.
1
0.1021/ol0600178 CCC: $33.50
© 2006 American Chemical Society
Published on Web 02/07/2006

N-heterocycles,6g the inexpensive Chloramine-T (CT) is
7
found to be a good N unit. A few examples of the
1
Table 2. Addition of CT to Styrene Derivatives under CO
2
aminohalogenation of olefins with CT have been reported,
but the methods require a heavy metal catalyst and/or provide
8
very low yields. From these points of view, we report herein
2
on the unique CO -induced vicinal aminochlorination of
olefins with CT, which expands the utility of the potential
nitrogen source in organic synthesis.
yields (%)
When styrene was treated with CT (1 equiv) under an
atmosphere of nitrogen at room temperature for 6 h, no
reaction was observed (Table 1, entry 1). The presence of
entry
R
1
2
1
2
3
4
NO2
Cl
Me
(1b) 71
(1c) 74
(1d) 54
(1e) 0
(2b) 0
(2c) 0
(2d) 9
MeO
(2e) 76
Table 1. Addition of Chloramine-T (CT) to Styrene under CO
2
the addition reaction did not occur under pressure conditions
without contribution of CO , the reaction was conducted
under 30 atm of N to result in no reaction (Table 1, entry
2).
To investigate the active species of the reaction, p-
substituted styrenes were subjected to the aminochlorination
2
2
1
yield (%)
atmosphere
entry
solvent
(atm)
1a
2a
(Table 2). The addition reaction of CT to p-nitro- and
1
2
3
4
5
6
7
8
9
MeCN
MeCN
MeCN
Et2O
THF
CH2Cl2
PhH
PhH
PhH
PhH
PhH
PhH
N2 (1)
0
1
38
9
25
54
63
57
78
80
16
0
0
13
7
2
0
0
0
0
0
CO2 (1)
CO2 (30)
CO2 (30)
CO2 (30)
CO2 (30)
CO2 (30)
CO2 (50)
CO2 (20)
CO2 (10)
CO2 (5)
N2 (30)
a
Table 3. Aminochlorination of Olefins with CT under CO
2
a
1
1
1
0
1
2
0
0
0
a
Reaction time: 9 h.
2
CO permitted the desired aminochlorination to proceed,
giving a small amount of 1a as well as 2a in 13% yield after
treatment with aqueous Na SO (Table 1, entry 2). Interest-
ingly, increasing the pressure of CO to 30 atm not only
2
3
2
improved the total yield but also reversed the selectivity of
these products (Table 1, entry 3), though the drastic change
of the regioselectivity could not be explained at present. A
reaction was then conducted under 30 atm of CO
range of solvents, including ether, THF, CH
2
, using a
Cl , and
2
2
benzene. Among these solvents, benzene was found to be
the best solvent to give 1a as the sole regioisomer in 63%
yield (Table 1, entries 4-7). Although the use of 50 atm of
CO was not effective for the aminochlorination, decrease
2
of the pressure to 10 atm improved the efficiency of the
reaction, affording the desired 1a in 80% yield (Table 1,
entries 8-10). Unfortunately, the lower pressure of CO
2
(5
atm) gave a poor result (Table 1, entry 11). To confirm that
(
7) (a) Champbell, M. M.; Johnson, G. Chem. ReV. 1978, 78, 65-79.
b) Bremner, D. H. In Synthetic Reagents; Pizey, J. S., Ed.; Wiley: New
York, 1985; Vol. 6, pp 9-59.
8) (a) Barton, D. H. R.; Hay-Motherwell, R. S.; Motherwell, W. B. J.
Chem. Soc., Perkin Trans. 1 1983, 445-451. (b) Damin, B.; Garapon, J.;
Sillion, B. Tetrahedron Lett. 1980, 21, 1709-1710.
(
a
(
Reaction conditions: olefin (1 mmol), CT (1 mmol), CO2 (10 atm),
PhH (3 mL), rt, 6 h. b At 70 °C.
968
Org. Lett., Vol. 8, No. 5, 2006

1
0
chlorostyrene, in the presence of CO
2
, at a pressure of 10
a 1,4-adduct was obtained as the sole product in 70% yield
without the formation of any 1,2-adduct.
atm, proceeded regioselectively to give 1b and 1c, respec-
tively, in good yields (Table 2, entries 1 and 2), with the
same selectivity as that observed for styrene, as shown in
Table 1. In the aminochlorination of p-methylstyrene under
the same conditions, two regioisomers 1d and 2d were
obtained (Table 2, entry 3). p-Methoxystyrene was com-
pletely transformed to â-chlorinated 2e in 76% yield (Table
Scheme 1. 1,4-Addition of CT to 1,3-Cyclooctadiene under
CO
2
2, entry 4). These results indicate that the reaction might
proceed through an ionic species.
A variety of olefins were examined for aminochlorination
with CT under CO
of trans- and cis-â-methylstyrene proceeded in good yields
and complete regioselectivity, two diastereomers were
2
(Table 3). While the aminochlorination
In summary, a new type of aminohalogenation of olefins
has been developed using a unique combination of CT and
9
CO . The present method could be applied to a variety of
2
obtained with anti-selectivity in the same ratio, respectively.
R-Methylstyrene was also aminochlorinated to afford pre-
dominantly the R-chlorinated compound. The aromatic cyclic
olefins, indene and 1,2-dihydronaphthalene, were readily
converted to the corresponding anti-adducts with two regio-
isomers, where R-chloro derivatives were mainly produced.
Aliphatic olefins were found to be applicable to the reaction
as well, although the efficiency needs to be improved. An
electron-sufficient olefin, butyl vinyl ether, was a good
substrate for aminochlorination leading to a regiocontrolled
adduct.
olefins, including an electron-sufficient olefin and a conju-
gated diene. This unprecedented addition is heavy-metal-
free, noncatalytic, and is an atom-economical process. The
1
1
mechanistic consideration and the introduction of CO to
2
organic molecules based on this system is currently under-
way.
Acknowledgment. This work was partially supported by
a Grant-in-Aid for Scientific Research from the Japan Society
for the Promotion of Science. We also acknowledge partial
support from The Kansai Electric Power Company, Inc.
To demonstrate the utility of the system, the reaction of a
conjugated diene was examined. When 1,3-cyclooctadiene
was treated with CT under CO (10 atm) at 70 °C in benzene,
2
Supporting Information Available: Experimental details
and spectral data for the major products. This material is
available free of charge via the Internet at http://pubs.acs.org.
OL0600178
(9) The spectroscopic data of compounds 1f and 1g were in agreement
with those for the previously reported compounds. See: Flores-Parra, A.;
Su a´ rez-Moreno, P.; S a´ nchez-Ru ´ı z, S. A.; Tlahuextl, M.; Jaen-Gaspar, J.;
Tlahuext, H.; Salas-Coronado, R.; Cruz, A.; N o¨ th, H.; Contreras, R.
Tetrahedron: Asymmetry 1998, 9, 1661-1671.
(10) Although the stereochemistry of the product was not determined,
one isomer was obtained.
(11) Since the mechanism of the present reaction is very interesting, the
detail should be clarified in near future.
Org. Lett., Vol. 8, No. 5, 2006
969