Fan Zhenwei, Ye Mingxing, Wang Yahao, Qiu Jian, Li Wangyang, Ma Xingxing, Yang Kai, Song Qiuling
Key Laboratory of Molecule Synthesis and Function Discovery, Fujian Province University, College of Chemistry at Fuzhou University, Fuzhou, Fujian 350108, China.
Institute of Next Generation Matter Transformation, College of Material Sciences Engineering, Huaqiao University, Xiamen, Fujian 361021, China.
ACS Cent Sci. 2022 Aug 24;8(8):1134-1144. doi: 10.1021/acscentsci.2c00339. Epub 2022 Jul 20.
Fluorine-containing organoboron compounds have emerged as novel building blocks in chemical synthesis; among them, fluorinated sp/sp 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/sp diborylations of 1-chloro-1-trifluoromethylalkenes, leading to diborylated compounds bearing a -difluoroalkenyl moiety; most intriguingly, the new formed C-B bonds include one stereoselective and optically pure Csp-B bond. Further transformations on the eventual products demonstrated the values of our presented strategy.
含氟有机硼化合物已成为化学合成中的新型结构单元；其中，氟化sp/sp二硼化化合物特别引人注目，因为它们可能会使具有氟化官能团的不同碳-硼键发生化学选择性和多样化转化，从而为最终产物带来多样性和复杂性。然而，用于构建此类氟化二硼化化合物的便捷合成策略非常稀少。在此，我们披露了对映选择性铜催化的1-氯-1-三氟甲基烯烃的sp/sp二硼化反应，生成带有二氟烯基部分的二硼化化合物；最引人注目的是，新形成的碳-硼键包括一个立体选择性且光学纯的Csp-硼键。对最终产物的进一步转化证明了我们所提出策略的价值。
