Catalytic enantioselective desymmetrization of COT-monoepoxide. Maximum deviation from coplanarity for an SN2′-cuprate alkylation

Organic Letters

Volumn 5, Issue 11, 2003, Pages 1971-1974

  Del Moro, Federica ^a   Crotti, Paolo ^a   Di Bussolo, Valeria ^a   Macchia, Franco ^a   Pineschi, Mauro ^a  

^a UNIVERSITY OF PISA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

1,3,5,7 CYCLOOCTATETRAENE MONOEPOXIDE; COPPER DERIVATIVE; EPOXIDE; UNCLASSIFIED DRUG;

ALKYLATION; ARTICLE; CATALYSIS; CHEMICAL BOND; ENANTIOSELECTIVITY; ISOMERISM; RING OPENING; SYNTHESIS;

EID: 0141518295     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol034554t     Document Type: Article

References (37)

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18. In this paper, "lower order cuprate" and "higher order cuprate" terms are used to indicate the 1:1 and 2:1 composition of RMgX and CuCN, respectively. For a review regarding the structure and reactivity of cyanocuprates, see: Krause, N. Angew. Chem., Int. Ed. 1999, 38, 79. For a recent discussion about the strong influences by the composition of the reagents and the solvent used in a metal-catalyzed addition of Grignard reagents to allylic acetates, see: Ito, M.; Matsuumi, M.; Murugesh, M. G.; Kobayashi, Y. J. Org. Chem. 2001, 66, 5881 and references therein.
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31. This is a new way to obtain enantiomerically pure 2-alkyl-substituted cyclooctanols. The direct asymmetric ring opening of cyclooctene oxide remains a difficult challenge. For some recent reports, see: (a) Jacobsen, E. N. Acc. Chem. Res. 2000, 33, 421. (b) Denmark, S. E.; Barsanti, P. A.; Wong, K.-T.; Stavenger, R. A. J. Org. Chem. 1998, 63, 2428. (c) Denmark, S. E.; Wynn, T.; Jellerichs, B. G. Angew. Chem., Int. Ed. 2001, 40, 2225.
32. This is a new way to obtain enantiomerically pure 2-alkyl-substituted cyclooctanols. The direct asymmetric ring opening of cyclooctene oxide remains a difficult challenge. For some recent reports, see: (a) Jacobsen, E. N. Acc. Chem. Res. 2000, 33, 421. (b) Denmark, S. E.; Barsanti, P. A.; Wong, K.-T.; Stavenger, R. A. J. Org. Chem. 1998, 63, 2428. (c) Denmark, S. E.; Wynn, T.; Jellerichs, B. G. Angew. Chem., Int. Ed. 2001, 40, 2225.
33. In general, the prerequisite for an allylic alkylation to occur is the ability of the system to attain a conformation in which the π-orbitals of the double bond and the σ-bond connecting the leaving group are aligned. For example, see: Farthing, C. N.; Kocovsky, P. J. Am. Chem. Soc. 1998, 120, 6661 and pertinent references therein.
34. Corey, E. J.; Boaz, N. W. Tetrahedron Lett. 1984, 25, 3063. For a molecular orbital description of the effect of π-accepting ligands such as cyanide in cuprate reactions, see: Hamon, L.; Levisalles, J. Tetrahedron 1989, 45, 489.
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36. Maximum deviation tolerated from the perfect alignment seems to be ca. 30° (see ref 24).
37. 3 in MeOH.