New asymmetric construction of the benzylic quaternary stereogenic centre: an enantiocontrolled access to (-)-α-cuparenone

Abstract

An efficient and enantiocontrolled formal total synthesis of (-)-α-cuparenone has been accomplished by employing a new asymmetric construction methodology for formation of the benzylic quaternary stereogenic centre.

References

1. K. Fuji, Chem. Rev., 1993, 93, 2037.
2. T. Takemoto, M. Sodeoka, H. Sasai and M. Shibasaki, J. Am. Chem. Soc., 1993, 115, 8477.
3. For recent representative chiral syntheses of (–)-α-cuparenone; (a) A. I. Meyers and B. A. Lefker, J. Org. Chem., 1986, 51, 1541; (b) M. M. Gharpure and A. S. Rao, Synth. Commun., 1989, 19, 1813; (c) H. Nemoto, H. Ishibashi, M. Nagamochi and K. Fukumoto, J. Org. Chem., 1992, 57, 1707; (d) J. L. Canet, A. Fadel and J. Salaün, J. Org. Chem., 1992, 57, 3463 and references are cited therein. For (+)-α-cuparenone,; (e) T. Honda, N. Kimura and M. Tsubuki, Tetrahedron Asymmetry, 1993, 4, 21; (f) J. B. Schwarz and A. I. Meyers, J. Org. Chem., 1995, 60, 6511; (g) K. Maruoka, M. Oishi and H. Yamamoto, J. Am. Chem. Soc., 1996, 118, 2289.
4. For cyclopentene annulation via[1,5] C–H insertion of alkylidene carbene; (a) J. Wolinsky, G. W. Clark and P. C. Thorstenson, J. Org. Chem., 1976, 41, 745; (b) J. C. Gilbert, D. H. Giamalva and U. Weerasooriya, J. Org. Chem., 1983, 48, 5251; (c) J. C. Gilbert, D. H. Giamalva and M. E. Baze, J. Org. Chem., 1985, 50, 2557; (d) M. Ochiai, M. Kunishima, Y. Nagao, K. Fuji, M. Shiro and E. Fujita, J. Am. Chem. Soc., 1986, 108, 8281; (e) M. Ochiai, M. Kunishima, S. Tani and Y. Nagao, J. Am. Chem. Soc., 1991, 113, 3135; (f) S. Ohira, K. Okai and T. Moritani, J. Chem. Soc., Chem. Commun., 1992, 721; (g) M. Ochiai, K. Uemura and Y. Masaki, J. Am. Chem. Soc., 1993, 115, 2528; (h) S. Ohira, T. Moritani, T. Ida and M. Yamato, J. Chem. Soc., Chem. Commun., 1993, 1299; (i) R. R. Tykwinski, P. J. Stang and N. E. Persky, Tetrahedron Lett., 1994, 35, 23; (j) M. Kunishima, K. Hioki, S. Tani and A. Kato, Tetrahedron Lett., 1994, 35, 7253; (k) D. F. Taber and R. P. Meagley, Tetrahedron Lett., 1994, 35, 7909; (l) S. Kim and C. M. Cho, Tetrahedron Lett., 1994, 35, 8405; (m) D. F. Taber, A. Sahli, H. Yu and R. P. Meagley, J. Org. Chem., 1995, 60, 6571; (n) D. F. Taber, R. P. Meagley and D. J. Doren, J. Org. Chem., 1996, 61, 5723.
5. H. M. Sweers and C.-H. Wong, J. Am. Chem. Soc., 1986, 108, 6421; Y.-F. Wang and C.-H. Wong, J. Org. Chem., 1988, 53, 3127; Y.-F. Wang, J. J. Lalonde, M. Momongan, D. E. Bergbreiter and C.-H. Wong, J. Am. Chem. Soc., 1988, 110, 7200.
6. (a) S. Takano, K. Samizu and K. Ogasawara, Synlett, 1993, 393; (b) T. Sakamoto, Y. Kondo and H. Yamanaka, Heterocycles, 1993, 36, 2437; (c) Y. Koga, M. Sodeoka and M. Shibasaki, Tetrahedron Lett., 1994, 35, 1227.
7. H. Frauenrath, Synthesis, 1989, 721.
8. P. A. Levene and G. M. Meyer, Org. Synth., 1943, Coll. Vol. II, 288.
9. G. Guanti, E. Narisano, T. Podgorski, S. Thea and A. Williams, Tetrahedron, 1990, 46, 7081.
10. R. E. Dabby, J. Kenyon and R. F. Mason, J. Chem. Soc., 1952, 4881.
11. N. Chidambaram and S. Chandrasekaran, J. Org. Chem., 1987, 52, 5048.