LETTER
Michael Reactions of a-Nitroketones in Water
2161
Table 1 Results of the Michael Additions to a-Nitrocycloalkanones
Entry
Z
n
2
2
2
1
3
3
5
7
2
2
2
2
2
2
2
2
2
2
Product
3a
3b
3c
Conditions
Yield (%)
1
2
3
4
5
6
7
8
9
CHO
COCH3
H O, r.t., 8 h
85
93
85
98
99
98
99
99
30
40
76
65
92
80
49
55
60
77
2
H O, r.t., 4 d
2
COCH CH
H O, r.t., 4 d
2
3
2
CHO
CHO
COCH3
CHO
CHO
3d
3e
H O, r.t., 14 h
2
H O, r.t., 14 h
2
3f
H O, r.t., 4 d
2
3g
3h
3i
H O, r.t., 37 h
2
H O, r.t., CTAB (10%), 5 d
2
CO CH3
H O, r.t., 7 d
2
2
10
11
12
13
14
15
16
17
18
CO CH3
3i
H O, reflux, 1 d
2
2
COCH3
COCH3
COCH3
3b
3b
3b
3c
KHCO (0.07 M in H O), r.t., 3 h
3
2
K CO (0.035 M in H O), r.t., 4 h
2
3
2
K CO (0.07 M in H O), r.t., 30 min
2
3
2
COCH CH
K CO (0.07 M in H O), r.t., 1 h
2 3 2
2
3
CO CH3
3i
K CO (0.07 M in H O), r.t., 45 min
2 3 2
2
CHO
CN
3a
3j
K CO (0.07 M in H O), r.t., 30 min
2 3 2
K CO (0.07 M in H O), r.t., CTAB (10%), 3 h
2
3
2
SO C H
3k
K CO (0.07 M in H O), r.t., CTAB (10%), 3 h
2 3 2
2
6
5
References
(12) Barrett, A. G. M.; Spilling, C. D. Tetrahedron Lett. 1988, 29,
733.
13) (a) Bergman, E. D.; Ginsburg, D.; Pappo, R. Org. React.
959, 10, 1795. (b) Jung, M. E.; Semmelhack, M. F.
Comprehensive Organic Synthesis, Vol. 4; Trost, B. M.;
Fleming, I., Eds.; Pergamon Press: Oxford, 1991, 1–67.
14) (a) Ballini, R.; Papa, F.; Abate, C. Eur. J. Org. Chem. 1999,
5
(
1) (a) Li, C.-J. Chem. Rev. 1993, 93, 2023. (b) Chan, T. H.; Li,
C.-J. Can. J. Chem. 1994, 72, 1181. (c) Lubineau, A.; Augé,
J.; Queneau, Y. Synthesis 1994, 741. (d) Li, C.-J.; Chan, T.
H. Organic Reactions in Aqueous Media; Wiley: New York,
(
(
(
1
1
997. (e) Organic Synthesis in Water; Grieco, P. A., Ed.;
Blacky Academic and Professional: London, 1998.
f) Lubineau, A.; Augé, J. Topics in Current Chemistry, In
87. (b) Ballini, R.; Barboni, L.; Bosica, G. J. Org. Chem.
(
2000, 65, 6261. (c) Ballini, R.; Barboni, L.; Bosica, G.;
Modern Solvents in Organic Synthesis, Vol. 206; Knochel,
P., Ed.; Springer-Verlag: Berlin, Heidelberg, 1999, 1.
2) Ribe, S.; Wipf, P. Chem. Commun. 2001, 299.
3) Ludwig, R. Angew. Chem. Int. Ed. 2001, 40, 1808.
4) Keller, E.; Feringa, B. L. Synlett 1997, 842.
Filippone, P.; Peretti, S. Tetrahedron 2000, 56, 4095.
15) (a) Cookson, R. C.; Ray, P. S. Tetrahedron Lett. 1982, 23,
(
(
(
(
3521. (b) Yurdakul, A.; Gurtner, C.; Jung, E.-S.; Lorenzi-
Riatsch, A.; Linden, A.; Guggisberg, A.; Bienz, S.; Hesse,
M. Helv. Chim. Acta 1998, 81, 1373. (c) Ballini, R.;
5) Mori, Y.; Kakumoto, K.; Manabe, K.; Kobayashi, S.
Tetrahedron Lett. 2000, 41, 3107.
Barboni, L.; Bosica, L.; Fiorini, D. Synthesis 2002, 2725.
16) (a) Rosini, G.; Ballini, R.; Marotta, E. Tetrahedron 1989, 45,
(
(6) Shibatomi, K.; Nakahashi, T.; Uozomi, Y. Synlett 2000,
5935. (b) Ballini, R.; Petrini, M.; Rosini, G. Tetrahedron
1
643.
7) Bensa, D.; Brunel, J.-M.; Buono, G.; Rodriguez, J. Synlett
001, 715.
1990, 46, 7531.
(
(
(
17) Rosini, G.; Marotta, E. Synthesis 1986, 237.
18) These starting materials were prepared in two steps, by
transformation of commercially available cycloalkanones
into the enol acetates and subsequent treatment of the latter
compounds with acetyl nitrate.
2
(
(
8) Fischer, R. H.; Witz, H. M. Synthesis 1980, 261.
9) For a review, see: Ballini, R. Synlett 1999, 1009.
(
(
10) (a) Rosini, G.; Ballini, R.; Marotta, E. Tetrahedron 1989, 45,
5935. (b) Ballini, R.; Petrini, M.; Rosini, G. Tetrahedron
Representative Procedure: To a solution of cyclo-
heptanone (10 g, 90 mmol) in isopropenyl acetate (85 mL)
was added p-toluenesulfonic acid (2.9 g, 15 mmol). The
reacting mixture was refluxed for 24 h in an oil bath at
1990, 46, 7531.
11) Ballini, R.; Bosica, G.; Marcantoni, E.; Vita, P.; Bartoli, G.
J. Org. Chem. 2000, 65, 5845.
1
00 °C, and then it was cooled and diluted with Et O
2
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