文献类型：期刊文献

英文题名：Photoinduced Low-Valent Zirconium Catalysis for Cross-Electrophile Coupling of Ethers

作者：Guo, Ping[1,2];Song, Xuedong[1,2];Huang, Banruo[3];Zhang, Ruixue[1,2];Zhao, Jie[1,2]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, Shanghai 200237, Peoples R China;[3]Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

年份：2024

卷号：63

期号：32

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20242816680167);WOS:【SCI-EXPANDED(收录号:WOS:001264853900001)，CCR-EXPANDED(收录号:WOS:001264853900001)】；

基金：We thank prof. F. Dean Toste (U.C. Berkeley), prof. Mark Levin (U. Chicago) and prof. Bijie Li (Tsinghua U.) for helpful discussions. J.Z. thanks Shanghai Municipal Science and Technology Major Project (2018SHZDZX03), The Program of Introducing Talents of Discipline to Universities (B16017) and The National Natural Science Foundation of China (22301076) for funding support.

语种：英文

外文关键词：Zirconium; photoinduced; C-O bonds; cross-electrophile coupling; ether

摘要：Accessing versatile C(sp3)-C(sp3) bond through the cross-electrophile coupling of two distinct etheric C-O bonds is crucial in organic synthesis but remains barely explored. Herein, we report an innovative photoinduced low-valent zirconocene catalysis enabling the reductive coupling of ethers with high activity and cross-selectivity. Mechanistic investigation suggests that photoexcitation of low-valent zirconocene facilitates the C(sp3)-O bond scission of benzylic ethers, leading to the benzylic radicals intermediate via a single-electron reduction pathway. The subsequent recombination of this benzylic radical with the Zr center followed by carbomagnesiation generates benzylic Grignard reagents for downstream coupling with aliphatic ethers through an SN2-like mechanism. In application, a wide range of ethers readily in situ derived from aldehydes and ketones becomes feasible with high functional group compatibility as well as excellent cross-selectivity. Photoinduced zirconocene catalysis was utilized to achieve the reductive coupling of ethers with remarkable activity and cross-selectivity. Mechanistic investigation revealed that photoexcitation of low-valent zirconocene facilitates the scission of benzylic C(sp3)-O bonds, resulting in benzylic radicals that recombine with Zr center. Subsequent carbomagnesiation generates benzylic Grignard reagents for downstream coupling with aliphatic ethers. image