Asymmetric induction via short-lived chiral enolates with a chiral C-O axis

Journal of the American Chemical Society

Volumn 135, Issue 19, 2013, Pages 7102-7105

  Yoshimura, Tomoyuki ^a   Tomohara, Keisuke ^a   Kawabata, Takeo ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL ARYL ETHERS; ASYMMETRIC INDUCTION; CYCLIC ETHER; ENOLATE INTERMEDIATES; ENOLATES;

ETHERS; REACTION INTERMEDIATES;

OLEFINS;

CARBON; ENOLATE DERIVATIVE; ETHER DERIVATIVE; OXYGEN; UNCLASSIFIED DRUG;

ALKYLATION; ARTICLE; CYCLIZATION; HALF LIFE TIME; RACEMIZATION;

EID: 84877831287     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja4018122     Document Type: Article

References (34)

1. Kawabata, T.; Suzuki, H.; Nagae, Y.; Fuji, K. Angew. Chem., Int. Ed. 2000, 39, 2155-2157
2. Kawabata, T.; Kawakami, S.; Majumdar, S. J. Am. Chem. Soc. 2003, 125, 13012-13013
3. Kawabata, T.; Matsuda, S.; Kawakami, S.; Monguchi, D.; Moriyama, K. J. Am. Chem. Soc. 2006, 128, 15394-15395
4. Kawabata, T.; Moriyama, K.; Kawakami, S.; Tsubaki, K. J. Am. Chem. Soc. 2008, 130, 4153-4157
5. Watanabe, H.; Yoshimura, T.; Kawakami, S.; Sasamori, T.; Tokitoh, N.; Kawabata, T. Chem. Commun. 2012, 48, 5346-5348
6. Zhao, H.; Hsu, D. C.; Carlier, P. R. Synthesis 2005, 1-16
7. Kawabata, T. Asymmetric Synthesis and Application of α-Amino Acids; ACS Symposium Series 1009; American Chemical Society: Washington, DC, 2009; pp 31-56.
8. Carlier, P. R.; Hsu, D. C.; Bryson, S. A. In Topics in Stereochemistry; Denmark, S. E., Ed.; John Wiley & Sons: New York, 2010; Vol. 26, pp 53-92. For recent reports on the asymmetric reactions via axially chiral enolates, see
9. Mai, T. T.; Viswambharan, B.; Gori, D.; Kouklovsky, C.; Alezra, V. J. Org. Chem. 2012, 77, 8797-8801
10. Mai, T. T.; Branca, M.; Gori, D.; Guillot, R.; Kouklovsky, C.; Alezra, V. Angew. Chem., Int. Ed. 2012, 51, 4981-4984
11. Fletcher, S. P.; Solá, J.; Holt, D.; Brown, R. A.; Clayden, J. Beilstein J. Org. Chem. 2011, 7, 1304-1309
12. Branca, M.; Pena, S.; Guillot, R.; Gori, D.; Alezra, V.; Kouklovsky, C. J. Am. Chem. Soc. 2009, 131, 10711-10718
13. Kolaczkowski, L.; Barnes, D. M. Org. Lett. 2007, 9, 3029-3032
14. MacQuarrie-Hunter, S.; Carlier, P. R. Org. Lett. 2005, 7, 5305-5308
15. Gerona-Navarro, G.; Bonache, M. A.; Hernz, R.; García- López, M. T.; González-Muñiz, R. J. Org. Chem. 2001, 66, 3538-3547
16. Kawabata, T.; Yahiro, K.; Fuji, K. J. Am. Chem. Soc. 1991, 114, 9694-9696
17. Still, W. C.; Streekumar, C. J. Am. Chem. Soc. 1980, 102, 1201-1202
18. Hoppe, D.; Hense, T. Angew. Chem., Int. Ed. 1997, 36, 2282-2316
19. Baek, P.; Basu, A.; Gallagher, D. J.; Pack, Y. S.; Thayumanavan, S. Acc. Chem. Res. 1996, 29, 552-560
20. Fuji, K.; Oka, T.; Kawabata, T.; Kinoshita, T. Tetrahedron Lett. 1998, 39, 1373-1374
21. Betson, M. S.; Clayden, J.; Worrall, C. P.; Peace, S. Angew. Chem., Int. Ed. 2006, 45, 5803-5807
22. Dramatic temperature effects in alkylation reactions of benzodiazepine enolates via memory of chirality has been reported. See ref 2i and Carlier, P. R.; Zhao, H.; MacQarrie-Hunter, S. L.; DeGuzman, J. C.; Hsu, D. C. J. Am. Chem. Soc. 2006, 128, 15215-15220
23. Uozumi, Y.; Kato, K.; Hayashi, T. J. Am. Chem. Soc. 1997, 119, 5063-5064
24. The importance of chelation may be suggested by the decrease in the enantioselectivity of the asymmetric cyclization of 2b in the presence of 15-crown-5. Treatment of 2b under conditions identical to those in entry 6 of Table 1, except for the addition of 15-crown-5 (3.0 equiv, gave 3b in 30% ee and 72% yield. A similar chelating effect on the stereochemistry of enolate alkylation was reported. See: Williams, R. M.; Glinka, T.; Kwast, E. J. Am. Chem. Soc. 1988, 110, 5927-5929
25. 2-I) of the chiral enolates generated from 7d-g may be in close proximity to the nucleophilic enolate moiety due to the buttressing effect of the substituent at C(3), which facilitates intramolecular alkylation before complete racemization of the chiral enolate takes place. For the detailed discussion, see Supporting Information (Scheme SI-1). The rate acceleration by the buttressing effect of the ortho substituent in carbene C-H insertion has been reported. See: Tomioka, H.; Kimoto, K.; Murata, H.; Izawa, Y. J. Chem. Soc., Perkin Trans. 1 1991, 471-477
26. Xie, L.; Isenberger, K. M.; Held, G.; Dahl, L. M. J. Org. Chem. 1997, 62, 7516-7519
27. Yabuuchi, T.; Kusumi, T. J. Org. Chem. 2000, 65, 397-404
28. Uozumi, Y.; Kyota, H.; Kato, K.; Ogasawara, M.; Hayashi, T. J. Org. Chem. 1999, 64, 1620-1625
29. Torraca, K. E.; Kuwabe, S.; Buchwald, S. L. J. Am. Chem. Soc. 2000, 122, 12907-12908
30. Trost, B. M.; Shen, H. C.; Dong, L.; Surivet, J.-P. J. Am. Chem. Soc. 2003, 125, 9276-9277
31. Mayer, G.; Taberner, P. V. Eur. J. Pharmacol. 2002, 454, 95-102
32. Cohen, J. L.; Limon, A.; Miledi, R.; Chamberlin, A. R. Bioorg. Med. Chem. Lett. 2006, 16, 2189-2194
33. Grisar, J. M.; Petty, M. A.; Bolkenius, F. N.; Dow, J.; Wagner, J.; Wagner, E. R.; Haegele, K. D.; De Jong, W. J. Med. Chem. 1991, 34, 257-260
34. Grisar, J. M.; Marciniak, G.; Bolkenius, F. N.; Verne-Mismer, J.; Wagner, J.; Wagner, E. R. J. Med. Chem. 1995, 38, 2880-2886