We describe in this account our progress towards the development of new catalytic asymmetric cross-coupling reactions. We focus on the application of boronic acids in the synthesis of enantioenriched C(sp2)–C(sp3) coupled products from prochiral and racemic starting materials. Specifically, we describe the rhodium-catalyzed Suzuki–Miyaura-type arylations of allylic halides and cyclobutenes, their key mechanistic features, and their applications to complex-molecule synthesis and scale-up.
