Lewis acid-catalyzed conjugate additions of silyloxyallenes: a selective solution to the intermolecular Rauhut-Currier problem

Silyloxyallenes serve as highly useful alpha-acylvinyl anion equivalents. These latent allenolates undergo conjugate additions to alkylidene malonates in the presence of 10 mol % Sc(OTf) 3. The reaction delivers intermolecular Rauhut-Currier products in excellent yields and regioselectivities for a wide scope of substrates. Notably, the formal cross-coupling of two different alpha,beta-unsaturated carbonyl compounds (a cross Rauhut-Currier reaction) is achieved. Preliminary investigations have demonstrated good levels of enantioselectivity for the addition of a racemic silyloxyallene with a chiral Lewis acid.