Iwasaki Takanori, Kambe Nobuaki
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
Research Center for Environmental Preservation, Osaka University, 2-4 Yamadaoka, Suita, Osaka, 565-0871, Japan.
Chem Rec. 2023 Sep;23(9):e202300033. doi: 10.1002/tcr.202300033. Epub 2023 Apr 18.
Carbon-fluorine bonds are stable and have demonstrated sluggishness against various chemical manipulations. However, selective transformations of C-F bonds can be achieved by developing appropriate conditions as useful synthetic methods in organic chemistry. This review focuses on C-C bond formation at monofluorinated sp -hybridized carbons via C-F bond cleavage, including cross-coupling and multi-component coupling reactions. The C-F bond cleavage mechanisms on the sp -hybridized carbon centers can be primarily categorized into three types: Lewis acids promoted F atom elimination to generate carbocation intermediates; nucleophilic substitution with metal or carbon nucleophiles supported by the activation of C-F bonds by coordination of Lewis acids; and the cleavage of C-F bonds via a single electron transfer. The characteristic features of alkyl fluorides, in comparison with other (pseudo)halides as promising electrophilic coupling counterparts, are also discussed.
碳氟键很稳定，并且已证明其对各种化学操作反应迟缓。然而，通过开发合适的条件，碳氟键的选择性转化可以实现，这在有机化学中是有用的合成方法。本综述重点关注通过碳氟键裂解在单氟取代的sp杂化碳上形成碳 - 碳键，包括交叉偶联和多组分偶联反应。sp杂化碳中心上的碳氟键裂解机制主要可分为三种类型：路易斯酸促进氟原子消除以生成碳正离子中间体；通过路易斯酸配位激活碳氟键，由金属或碳亲核试剂进行亲核取代；以及通过单电子转移裂解碳氟键。还讨论了与其他作为有前景的亲电偶联对应物的（拟）卤化物相比，烷基氟化物的特征。
