Secondary Allyltitanium(IV) Reagents in Aldehyde Allylation I: Extension of the Hoppe Reaction to γ-Alkoxy Secondary Allyl Carbamates

Abstract

An efficient access to optically active (R)- or (S)-γ-alkoxy allyltitanium(IV) intermediates, in aldehyde allylation reactions, is described. Enantiomeric γ-alkoxy secondary allyl carbamates (R)- and (S)-14 were first prepared. Determination of their enantiomeric excess was realised on the corresponding deuterated isotopic derivatives by NMR in chiral liquid media. Subsequent aldehyde allylation reaction with propanal performed under Hoppe n-BuLi·(-)-sparteine/Ti(Oi-Pr)₄ or n-BuLi·TMEDA/Ti(Oi-Pr)₄ con­ditions, led to both enantiomeric homoallylic alcohols 15 or ent-15 in 90% yield, 100% ed and 80% ee.

Key words

Hoppe allylation - allyltitanium reagent - ¹H NMR chiral nematic solvent - Sharpless resolution

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