Yu Teng, Yu‐Tao Xue, Mengqiang Cai, Y L Zhong, Hong‐Shuang Li
An unprecedented Pd(II)‐catalyzed defluorinative chalcogenation of gem ‐difluorocyclopropanes has been developed. The coupling reactions of selenols (or their surrogates) and thiols with the strained fluorinated three‐membered ring lead to the formation of 2‐fluoroallylic chalcogenides with good regio‐ and stereoselectivity, which cannot be accessed through conventional approaches. This ring‐opening transformation exhibits remarkable atom economy and a broad substrate scope, offers suitability for scale‐up synthesis, and thereby provides a straightforward and promising avenue for the construction of chalcogen‐ and fluorine‐containing privileged scaffolds.