Chiral Phosphoric Acid Dual-Function Catalysis: Asymmetric Allylation with α-Vinyl Allylboron Reagents.

We report a dual function asymmetric catalysis by a chiral phosphoric acid catalyst that controls both enantioselective addition of an achiral α-vinyl allylboronate to aldehydes and pseudo-axial orientation of the α-vinyl group in the transition state. The reaction produces dienyl homoallylic alcohols with high Z-selectivities and enantioselectivities. Computational studies revealed that minimization of steric interactions between the alkyl groups of the diol on boron and the chiral phosphoric acid catalyst influence the orientation of α-vinyl substituent of the allylboronate reagent to occupy a pseudo-axial position in the transition state.