安徽农业大学曹志超/南工大赵莉莉ACIE:镍催化通过烯基C-O键的Z式选择性官能团化反应实现苯并呋喃的阻转异构选择性去芳构化交叉偶联反应
Catalytic asymmetric transformation of benzofuran derivatives has received significant attention owing to its capacity to prepare chiral molecules from readily available feedstocks. Herein, an unprecedented asymmetric cross-coupling of benzofuran derivatives is reported for the construction of axial chirality. Employing a chiral nickel catalyst, this approach is achieved through direct enantio- and Z-selective dearomative functionalization of the vinyl C─O bond, providing efficient access to valuable atropisomeric acyclic alkenes. A broad substrate scope is demonstrated under mild conditions. Moreover, experimental and theoretical mechanistic studies suggest that the stereochemical outcome is facilitated by a dynamic epimerization between diastereomeric six-membered (Z)-styryl-nickelacycle intermediates.图4. 苯并呋喃衍生物底物范围 (图片来源于ACIE)图6. 放大反应和合成转化反应 (图片来源于ACIE)图7. 机理研究及可能的催化循环 (图片来源于ACIE)In summary, we have demonstrated an atroposelective dearomative cross-coupling of readily available benzofuran derivatives for the construction of axial chirality for the first time. Enabled by a chiral nickel catalyst, this transformation proceeded via direct enantio- and Z-selective functionalization of the vinyl C─O bond. This strategy provided streamlined access to a diverse array of valuable axially chiral acyclic alkenes. Comprehensive experimental and theoretical mechanistic studies were performed and supported that stereochemical outcome is enabled by the catalyst-controlled dynamic epimerization between two diastere omeric six-membered (Z)-styryl-nickelacycle intermediates. This method was characterized by its wide substrate scope and mild reaction conditions. Efforts to enhance the reaction efficiency and expand this mechanistic framework into dynamic kinetic asymmetric transformations are underway.DOI: doi.org/10.1002/anie.2984592声明：本文中广告内容由广告主提供，请您在购买任何商品或服务前，以书面合同形式明确约定双方权利义务，本账号不对其后续经营行为承担持续担保责任
