LETTER
Intermolecular Radical Carbon-Carbon Bond Forming Reaction in Water
1525
Table 3 Radical Addition Reactions of Cyclohexyl Iodide to Various Alkenes with EPHP (3 equiv) in the Presence of CTAB (1 equiv) in H O
2
X
I
EPHP, CTAB
+
X
Initiator, H O
2
X = SO Ph,
2
C(O)R,
CN,
C(O)OR
Entry
1
Alkene
Equiv of Alkene
Initiator (equiv)
ABCVA (0.25)
Temp. (°C)
80
Time (h)
1.5
Yield (%)
81
1
SO Ph
2
2
1
1
1
1
ABCVA (0.25)
ABCVA (0.25)
ABCVA (0.25)
ABCVA (0.25)
100
80
0.5
1.5
2
94
43
53
70
SO Ph
2
3a
4b
5
SO Ph
2
100
75
SO Ph
2
1.5
C(O)OCH3
CN
6
7
3
3
ABCVA (0.25)
ABCVA (0.5)
70
80
1.5
2.5
81
81
C(O)CH
3
8
9
3
1
ABCVA (1.0)
80
25
25
10
4
0
CN
Et B (1.0)
85
3
SO Ph
2
1
0
10
Et B (1.0)
4
63 (13)c
O
3
a
b
c
Without using CTAB.
Equiv of EPHP was used.
-Ethylcyclohexanone.
1
3
References
(4) (a) Jang, D. O. Tetrahedron Lett. 1996, 37, 5367. (b) Kita,
Y.; Nambu, H.; Ramesh, N. G.; Anikumar, G.; Matsugi, M.
Org. Lett. 2001, 3, 1157. (c) Jang, D. O.; Cho, D. Y. Synlett
(1) (a) Giese, B. Radicals in Organic Synthesis: Formation of
Carbon-Carbon Bonds; Pergamon Press: Oxford, 1986.
2
002, 631.
5) (a) Graham, A. E.; Thomas, A. V.; Yang, R. J. Org. Chem.
000, 65, 2583. (b) Yorimitsu, H.; Shinokubo, H.; Oshima,
(
b) Curran, D. P. Synthesis 1988, 417. (c) Curran, D. P.
(
Synthesis 1988, 479. (d) Curran, D. P. In Comprehensive
Organic Synthesis, Vol. 4; Trost, B. M.; Fleming, I., Eds.;
Pergamon: Oxford, 1991, 715. (e) Motherwell, W.; Crich,
D. Free Radical Chain Reactions in Organic Synthesis;
Academic Press: London, 1992.
2
K. Chem. Lett. 2000, 105. (c) Yorimitsu, H.; Shinokubo, H.;
Oshima, K. Bull. Chem. Soc. Jpn. 2001, 74, 225.
(
6) (a) Minisci, F. Synthesis 1973, 1. (b) Breslow, R.; Light, J.
Tetrahedron Lett. 1990, 31, 2957. (c) Yamazaki, O.; Togo,
H.; Nogami, G.; Yokoyama, M. Bull. Chem. Soc. Jpn. 1997,
(
2) For recent reviews: (a) Baguley, P. A.; Walton, J. C. Angew.
Chem. Int. Ed. 1998, 37, 3072. (b) Studer, A.; Amrein, S.
Synthesis 2002, 835.
70, 2519. (d) Maitra, U.; Sarma, K. D. Tetrahedron Lett.
1994, 35, 7861. (e) Nambu, H.; Hata, K.; Matsugi, M.; Kita,
(
3) (a) Barton, D. H. R.; Jang, D. O.; Jaszberenyi, J. C.
Tetrahedron Lett. 1992, 33, 5709. (b) Barton, D. H. R.;
Jang, D. O.; Jaszberenyi, J. C. J. Org. Chem. 1993, 58,
Y. Chem. Commun. 2002, 1082. (f) For a recent review:
Yorimitsu, H.; Shinokubo, H.; Oshima, K. Synlett 2002, 674.
7) (a) Li, C.-J.; Chan, T.-H. Organic Reactions in Aqueous
Media; John Wiley and Sons: New York, 1997. (b) Grieco,
P. A. Organic Synthesis in Water; Blackie Academic and
Professional: London, 1998. (c) Lubineau, A.; Auge, J. In
Modern Solvents in Organic Synthesis; Knochel, P., Ed.;
Springer-Verlag: Berlin, 1999.
(
6
838. (c) McCague, R.; Pritchard, R. G.; Stoodley, R. J.;
Williamson, D. S. Chem. Commun. 1998, 2691.
d) Tokuyama, H.; Yamashita, T.; Reding, M. T.; Kaburagi,
Y.; Fukuyama, T. J. Am. Chem. Soc. 1999, 121, 3791.
e) Graham, S. R.; Murphy, J. A.; Coates, D. Tetrahedron
(
(
Lett. 1999, 40, 2415. (f) Graham, S. R.; Murphy, J. A.;
Kennedy, A. R. J. Chem. Soc., Perkin Trans. 1 1999, 3071.
4b
(
8) For intramolecular C-C bond formation in water, see ref.
(
9) Brown, H. C.; Midland, M. M. Angew. Chem., Int. Ed. Engl.
(g) Jang, D. O.; Song, S. H. Tetrahedron Lett. 2000, 41, 247.
1972, 11, 692.
(
h) Concepcion, G. M.; Murphy, J. A.; Christopher, R. S.
Tetrahedron Lett. 2000, 41, 1833. (i) Takamatsu, S.;
Katayama, S.; Hirose, N.; Naito, M.; Izawa, K. Tetrahedron
Lett. 2001, 42, 7605. (j) Jang, D. O.; Cho, D. Y.; Chung,
C.-M. Synlett 2001, 1923.
Synlett 2002, No. 9, 1523–1525 ISSN 0936-5214 © Thieme Stuttgart · New York