Zeng Yaxin, Xia Ying
West China School of Public Health and West China Fourth Hospital, West China-PUMC C.C. Chen Institute of Health, State Key Laboratory of Biotherapy, Sichuan University, 610041, Chengdu, China.
Angew Chem Int Ed Engl. 2023 Aug 7;62(32):e202307129. doi: 10.1002/anie.202307129. Epub 2023 Jul 3.
Direct synthesis of gem-difluorinated carbocyclic molecules represents a longstanding challenge in organic chemistry. Herein, a Rh-catalyzed [3+2] cycloaddition reaction between readily available gem-difluorinated cyclopropanes (gem-DFCPs) and internal olefins has been developed, enabling the efficient synthesis of gem-difluorinated cyclopentanes with good functional group compatibility, excellent regioselectivity and good diastereoselectivity. The resulting gem-difluorinated products can undergo downstream transformations to access various mono-fluorinated cyclopentenes and cyclopentanes. This reaction demonstrates the use of gem-DFCPs as a type of "CF " C3 synthon for cycloaddition under transition metal catalysis, which provides potential strategy for synthesizing other gem-difluorinated carbocyclic molecules.
偕二氟代碳环分子的直接合成是有机化学中长期存在的挑战。在此，已开发出一种铑催化的、在易于获得的偕二氟代环丙烷（gem-DFCPs）与内烯烃之间的[3+2]环加成反应，能够高效合成具有良好官能团兼容性、出色区域选择性和良好非对映选择性的偕二氟代环戊烷。所得的偕二氟代产物可进行下游转化，以获得各种单氟代环戊烯和环戊烷。该反应证明了gem-DFCPs作为一种“CF₂ = C³”合成子在过渡金属催化下用于环加成反应，为合成其他偕二氟代碳环分子提供了潜在策略。
