2922
T. Katoh et al.
LETTER
(35), 124 (56), 101 (100), 58 (62); HRMS: m/z calcd for
Acknowledgment
C10H16O3 (M+): 184.1099, found: 184.1094.
(5) (a) Westerman, B.; Scharman, H. G.; Kortman, I.
Tetrahedron: Asymmetry 1993, 10, 2119. (b) Tomioka, K.;
Ando, K.; Takemasa, Y.; Koga, K. J. Am. Chem. Soc. 1984,
106, 2718.
This research was financially supported in part by Frontier Research
Program and the 21st Century Center of Excellence Program
‘Development of Drug Discovery Frontier Integrated from
Tradition to Proteome’ of the Ministry of Education, Culture, Sport,
and Technology, Japan.
(6) (1R)-(1-Methyl-2-oxocyclohexyl)carboxylic acid (60% ee)
prepared by PLE-catalyzed optical resolution of ethyl (1-
methyl-2-oxocyclohexyl)carboxylate5 was derivatized to
(1R,3R)- and (1R,3S)-methyl (1-methyl-2-oxocyclo-
hexyl)carboxylate; the direction of optical rotation [(+) for
cis isomer, and (–) for trans isomer] implied that the 2a-cis
and 2a-trans should have an R configuration at C-1.
(7) (a) Haworth, R. D.; Moore, B. P. J. Chem. Soc. 1946, 633.
(b) Mancini, V.; Fringuelli, F.; Taticci, A. Gazz. Chim. Ital.
1969, 99, 953. (c) Kanjilal, R. D.; Alam, S. K.; Ghatak, U.
R. Synth. Commun. 1981, 795. (d) Snider, B. B.; Mohan, R.;
Kates, S. A. J. Org. Chem. 1985, 50, 3659. (e) Meyer, W.
L.; Maheshwari, K. K. Tetrahedron Lett. 1964, 2175.
(f) Roy, A.; Paul, T.; Drew, M. G. B.; Mukherjee, D.
Tetrahedron Lett. 2003, 44, 4835.
References
(1) (a) Node, M.; Inoue, T.; Araki, M.; Nakamura, D.; Nishide,
K. Tetrahedron Lett. 1995, 36, 2255. (b) Katoh, T.; Kakiya,
K.; Nakai, T.; Nakamura, S.; Nishide, K.; Node, M.
Tetrahedron: Asymmetry 2002, 13, 2351. (c) Node, M.;
Inoue, T.; Araki, M.; Nakamura, D.; Nishide, K.
Tetrahedron: Asymmetry 1998, 9, 157. (d) Node, M.;
Nakamura, S.; Nakamura, D.; Katoh, T.; Nishide, K.
Tetrahedron Lett. 1999, 40, 5357.
(2) Pappo, R.; Allen, D. S. Jr.; Lemieux, R. U.; Johnson, W. S.
J. Org. Chem. 1956, 21, 478.
(3) Seebach, D.; Hungerbuhler, E.; Naef, R.; Schnurrenberger,
P.; Weidmann, B.; Zuger, M. Synthesis 1982, 138.
(4) As shown below, the singlet signal assigned to the a-methyl
group of 2a-cis appeared at lower magnetic field than that of
2a-trans, while methyl signals as doublets were observed at
almost the same chemical shift.
(8) Hao, X.-J.; Node, M.; Fuji, K. J. Chem. Soc., Perkin Trans.
1 1992, 1505.
(9) Corey, E. J.; Fuchs, P. L. Tetrahedron Lett. 1972, 3769.
(10) King, F. E.; King, T. J.; Topliss, J. G. J. Chem. Soc. 1957, 9,
719.
(11) Eaton P. E., Carlson G. R., Lee J. T.; J. Org. Chem.; 1973,
573.
2a-cis: [a]D +69.6 (c 1.19, CHCl3, 84% ee); IR (CHCl3):
2951, 1736, 1705, 1458, 1273 cm–1; 1H NMR (400 MHz,
CDCl3): d = 3.74 (s, 3 H), 2.71–2.59 (m, 1 H), 2.46–2.45 (m,
1 H), 2.10–2.00 (m, 1 H), 1.90–1.78 (m, 3 H), 1.55–1.47 (m,
1 H), 1.47 (s, 3 H), 1.03 (d, J = 6.6 Hz, 3 H); MS (20 eV):
m/z (%) = 184 (M+, 20), 152 (20), 124 (37), 101 (100), 58
(34); HRMS: m/z calcd for C10H16O3 (M+): 184.1099, found:
184.1103.
2a-trans: [a]D –153 (c 0.80, CHCl3, 89% ee); IR (CHCl3):
2939, 1709, 1454, 1258 cm–1; 1H NMR (400 MHz, CDCl3):
d = 3.72 (s, 3 H), 2.59 (m, 2 H), 2.08–2.00 (m, 1 H), 1.76–
1.67 (m, 2 H), 1.46–1.30 (m, 2 H), 1.28 (s, 3 H), 1.05 (d,
J = 6.4 Hz, 3 H); MS (20 eV): m/z (%) = 184 (M+, 59), 152
(12) Recrystallization of 12 (258 mg, 84% ee) from n-hexane
afforded the optically pure compound (61.0 mg, >99.5%).
(13) (a) Nishide, K.; Ohsugi, S.; Fudesaka, M.; Kodama, S.;
Node, M. Tetrahedron Lett. 2002, 43, 5177. (b) Ohsugi, S.;
Nishide, K.; Oono, K.; Okuyama, K.; Fudesaka, M.;
Kodama, S.; Node, M. Tetrahedron 2003, 59, 8393.
(c) Nishide, K.; Ohsugi, S.; Miyamoto, T.; Kumar, K.; Node,
M. Monatsh. Chem. 2004, 135, 189.
(14) Mancini, V.; Fringuelli, F.; Taticchi, A. Gazz. Chim. Ital.
1969, 99, 953.
Synlett 2005, No. 19, 2919–2922 © Thieme Stuttgart · New York