Boryl radical catalysis enables asymmetric radical cycloisomerization reactions

作者：Chang-Ling Wang, Jie Wang, Ji‐Kang Jin, Bin Li, Yee Lin Phang, Feng‐Lian Zhang, Ye Tian, Huimin Xia, Li-Wen Hui, Ji‐Hu Su, Yao Fu, Yi‐Feng Wang · 发表于：Science · 年份：2023 · DOI：10.1126/science.adg1322 · 被引用次数：76 · 研究领域：Catalytic C–H Functionalization Methods、Radical Photochemical Reactions、N-Heterocyclic Carbenes in Organic and Inorganic Chemistry

The development of functionally distinct catalysts for enantioselective synthesis is a prominent yet challenging goal of synthetic chemistry. In this work, we report a family of chiral N -heterocyclic carbene (NHC)–ligated boryl radicals as catalysts that enable catalytic asymmetric radical cycloisomerization reactions. The radical catalysts can be generated from easily prepared NHC-borane complexes, and the broad availability of the chiral NHC component provides substantial benefits for stereochemical control. Mechanistic studies support a catalytic cycle comprising a sequence of boryl radical addition, hydrogen atom transfer, cyclization, and elimination of the boryl radical catalyst, wherein the chiral NHC subunit determines the enantioselectivity of the radical cyclization. This catalysis allows asymmetric construction of valuable chiral heterocyclic products from simple starting materials.