华中农业大学滕怀龙/武大孔望清ACIE:光-HAT/镍双催化实现区域、立体、对映选择性C(sp3)─H键单氟烯基化反应
Stereoselective functionalization of C(sp3)─H bonds in hydrocarbons constitutes a revolutionary strategy for accessing high value chiral molecules. Despite remarkable advances in this field, enantioselective C(sp3)-H monofluoroalkenylation remains unexplored to date. Herein, we report the first regio-, stereo-, and enantioselective benzylic C(sp3)─H monofluoroalkenylation, enabled by a decatungstate-mediated hydrogen atom transfer (HAT)/nickel dual-catalytic system. This protocol utilizes inexpensive, readily available hydrocarbons and easily accessible gem-difluoroalkenes as starting materials, delivering a broad array of structurally diverse (E)-monofluoroalkenes bearing stereogenic allylic centers, versatile building blocks in synthetic chemistry.图5. 偕二氟烯烃底物范围 (图片来源于ACIE)图6. 克级合成和合成转化反应 (图片来源于ACIE)In summary, we have developed a regio-, stereo-, and enantioselective monofluoroalkenylation of benzylic C(sp3)─H bonds with gem-difluoroalkenes via a decatungstate-mediated photoinduced hydrogen atom transfer/nickel dual catalysis. Employing cheap, readily available hydrocarbons and easily accessible gem-difluoroalkenes as starting materials, this protocol provides a general strategy for the efficient synthesis of a broad range of densely functionalized (E)-monofluoroalkenes bearing stereogenic allylic centers. Mechanistic investigations indicate that benzylic radicals generated via photo-HAT are captured by the nickel catalyst to form alkyl-nickel species, followed by chelation-assisted stereoselective C─F oxidative addition, and final reductive elimination to afford the target products. We anticipate this protocol will be of great value to the medicinal chemistry community, facilitating the accelerated development of therapeutics containing complex monofluoroalkene motifs.DOI: doi.org/10.1002/anie.1226201声明：本文中广告内容由广告主提供，请您在购买任何商品或服务前，以书面合同形式明确约定双方权利义务，本账号不对其后续经营行为承担持续担保责任
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