Generation and Application of (Diborylmethyl)zinc(II) Species: Access to Enantioenriched gem‐Diborylalkanes by an Asymmetric Allylic Substitution

We report the successful generation of (diborylmethyl)zinc(II) species by transmetallation beteween isolable (diborylmethyl)lithium and zinc(II) halide (X=Br, Cl) and their application in the synthesis of enantioenriched gem‐diborylalkanes bearing a stereogenic center at the β‐position of the diboryl groups by an asymmetric allylic substitution reaction. The reaction has a broad substrate scope, and various enantioenriched gem‐diborylalkanes can be obtained in good yields with excellent enantioselectivity. Further elaboration of the enantioenriched gem‐diborylalkanes provides access to a diverse set of valuable chiral building blocks.