Synthesis of All-Carbon Quaternary Stereocenters

Significance

Since Hayashi’s and Miyaura’s pioneering work on rhodium-catalyzed asymmetric 1,4-additions of boronic acids, the reaction has become a general and widely used synthetic transformation (see Review below). Construction of all-carbon quaternary stereocenters through this strategy is still challenging and was shown to work only with highly reactive nucleophiles and a limited scope of electrophilic acceptors. In this work, the authors demonstrate a viable protocol for this transformation using tetraarylborates as the nucleophile source. An enantioselective reaction relying on a chiral diene ligand is presented.

Review: T. Hayashi, K. Yamasaki Chem. Rev. 2003, 103, 169-196.