Face selectivity in the reactions of 2,4-disubstituted adamantanes and their modification by inclusion in beta-cyclodextrin solutions

Abstract

Sodium borohydride reduction reactions on 4-X-adamantan-2-ones (where X=ethyleneketal 11, ethylenethioketal 12, and methylene 15) were studied, which gave Z-alcohols 16 and 17 (from en-face attack) as the predominant products for ketones 11 and 12, but gave 1: 1 mixture of Z- and E-18 alcohols for ketone 15. The en/zu face selectivity of 15 in sodium borohydride reduction was enhanced to 32/68 in beta-CD solution. Both 1,3-dipolar addition and dichlorocarbene addition reactions on 4-ethyleneketal-2-methyleneadamantane 13 underwent again predominant en-face attack to give products in an E/Z ratio of > 99:1 and 92:8, respectively. The exceptional high zu-face selectivity on the dichlorocarbene addition reaction of 15 may be explained by a temporal complexation between the carbene and the C-4-oxo group. In the epoxidation reaction of 13 and 15 the zu-face attack products were favored despite their steric congestions suggesting that hydrogen bonding interaction between the peroxide reagent and the C-4-oxo or 4-ethyleneketal is involved. (C) 2004 Elsevier Ltd. All rights reserved.