REGIOSELECTIVE FUNCTIONALIZATION OF cis-BICYCLO|3.3.0|OCTENONE DERIVATIVES. OXYMERCURATION/REDUCTION versus HYDROBORATION/OXIDATION. ACETAL GROUPS AS REGIO- AND STEREOSELECTIVE CONTROL ELEMENTS

Abstract
Cyclic acetal groups at the position 8 of the cis-bicyclo|3.3.0|octane system may act as regio- and stereoselective control elements, respectively, in hydroboration and oxymercuration reactions. Whereas the regioselectivity observed in hydroborations must be ascribed to homoallylic inductive effects, and leads predominantly to exo, 1,3-bifunctional relationships, the effect of acetal group in oxymercuration is mainly stereoselective due to coordination of mercury acetate with the nonbonding electron pairs of the endo-oxygen atom of the acetal group, and leads predominantly to exo, 1,4-bifunctional relationships.

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