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Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols Using Palladium and a Chiral Phosphoric Acid.

Tomoya MiuraJunki NakahashiMasahiro Murakami
Published in: Angewandte Chemie (International ed. in English) (2017)
(E)-δ-Boryl-substituted anti-homoallylic alcohols are synthesized in a highly diastereo- and enantioselective manner from 1,1-di(boryl)alk-3-enes and aldehydes. Mechanistically, the reaction consists of 1) palladium-catalyzed double-bond transposition of the 1,1-di(boryl)alk-3-enes to 1,1-di(boryl)alk-2-enes, 2) chiral phosphoric acid catalyzed allylation of aldehydes, and 3) palladium-catalyzed geometrical isomerization from the Z to E isomer. As a result, the configurations of two chiral centers and one double bond are all controlled with high selectivity in a single reaction vessel.
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