Enantioselective Copper-Catalyzed sp(2)/sp(3) Diborylation of 1-Chloro-1-Trifluoromethylalkenes

[Image: see text] Fluorine-containing organoboron compounds have emerged as novel building blocks in chemical synthesis; among them, fluorinated sp(2)/sp(3) diborylated compounds are particularly appealing, since they might undergo chemoselective and diversified transformations of different C–B bonds with fluorinated functionality, thus bringing versatility and complexity to the eventual products. However, expedient, synthetic strategies for the construction of such fluorinated diborylative compounds are very sparse. Herein, we disclose enantioselective Cu-catalyzed sp(2)/sp(3) diborylations of 1-chloro-1-trifluoromethylalkenes, leading to diborylated compounds bearing a gem-difluoroalkenyl moiety; most intriguingly, the new formed C–B bonds include one stereoselective and optically pure Csp(3)–B bond. Further transformations on the eventual products demonstrated the values of our presented strategy.