An original­ syn: The first enantioselective Suzuki–Miyaura cross‐coupling of chiral, enantioenriched secondary allylic boronic esters is described (see scheme; DME=dimethoxyethane, Bpin = pinacolboryl, dba = dibenzylideneacetone). Mechanistic studies show that the reactions proceed via γ‐selective transmetalation followed by reductive elimination. The reaction provides the first independent confirmation that the transmetalation of boronic esters proceeds via a syn pathway.

The Suzuki‐Miyaura cross‐coupling of enantioenriched secondary allylic boronic esters occurs with high γ‐regioselectivity and high retention of chirality, proceeding via γ‐selective transmetalation and subsequent reductive elimination.