A solution to the unmet synthetic challenge of achieving highly atropo-enantioselective transestetification of Bringmann's lactones has been realized, employing a chiral bifunctional amine thiourea as promoter. The synergistic activation of the lactones,and alcohols/phenols by the respective thiourea and amine groups-is crucial for achieving the highly enantioselective, high-yielding dynamic kinetic resolution process: This protocol gives highly optically pure, axially chiral biaryl compounds with a broad substrate scope under mild reaction conditions.