[n]Dendralenes as a Platform for Selective Catalysis: Ligand-Controlled Cu-Catalyzed Chemo-, Regio-, and Enantioselective Borylations.

We report the development of two complementary methods for the Cu-catalyzed anti-Markovnikov borylation of one specific olefin in 2-substituted [n]dendralenes (n = 3-6). The first protocol operates with a bisphosphine ligand and occurs with high regio- and chemoselectivity for the terminal double bond, independently of the number of cross-conjugated alkenes. We show that the use of a chiral phosphanamine ligand enables the highly chemo-, regio-, and enantioselective borylation of the alkene cross-conjugated with the terminal olefin in [n]dendralenes.