State Key Laboratory of Structural Chemistry, Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, Fujian, 350002, P. R. of China.
University of Chinese Academy of Sciences, Beijing, 100049, P. R. of China.
Nat Commun. 2021 Nov 18;12(1):6670. doi: 10.1038/s41467-021-26843-2.
The straightforward strategy of building a chiral C-O bond directly on a general carbon radical center is challenging and stereocontrol of the reactions of open-chain hydrocarbon radicals remains a largely unsolved problem. Advance in this elementary step will spur the development of asymmetric radical C-O bond construction. Herein, we report a copper-catalyzed regioselective and enantioselective carboesterification of substituted dienes using alkyl diacyl peroxides as the source of both the carbon and oxygen substituents. The participation of external acids in this reaction substantially extends its applicability and leads to structurally diverse allylic ester products. This work represents the advance in the key elementary reaction of intermolecular enantioselective construction of C-O bond on open-chain hydrocarbon radicals and may lead to the discovery of other asymmetric radical reactions.
在一般的碳自由基中心上直接构建手性 C-O 键的直接策略具有挑战性，并且开链烃自由基反应的立体控制仍然是一个尚未解决的大问题。这一基本步骤的进展将促进不对称自由基 C-O 键构建的发展。在此，我们报道了一种铜催化的取代二烯的区域选择性和对映选择性的羧酯化反应，其中烷基二酰基过氧化物同时作为碳和氧取代基的来源。外部酸在该反应中的参与极大地扩展了其适用性，并得到了结构多样的烯丙基酯产物。这项工作代表了在开链烃自由基的分子间对映选择性 C-O 键构建的关键基本反应方面的进展，并可能导致其他不对称自由基反应的发现。
