Transition-metal-catalyzed asymmetricdefluorinative reactions

Danhua Ge,^*aJia-Wei Chen,^aYu-Lan Chen,^aMengtao Ma,^bZhi-Liang Shen^*aand Xue-Qiang Chu^*a

^aInstitute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China. E-mail: ias_zlshen@njtech.edu.cn; xueqiangchu@njtech.edu.cn.

^bDepartment of Chemistry and Materials Science, College of Science, NanjingForestry University, Nanjing 210037, China.

Abstract:Organofluorides have found wide applications in materials science, medicinal chemistry, agrochemistry, and organic synthesis. The unique reactivity and properties of fluorine-containing compounds renderthem worth investigating in asymmetric synthesis to access valuable enantioenriched molecules.Although metal catalysis paves the way for the chemoselective and regioselective defluorination offluorine-containing molecules, the functionalization of the elusive C–F bond integrated into catalyticenantioselective transformation remains highly sought after. In this review, the latest achievements intransition-metal-catalyzed enantioselective defluorinative coupling reactions have been comprehensivelysummarized on the basis of the classification of transition-metal catalysts. Compared with other heteroatoms, special emphasis is placed on the function of the fluorine atom as a detachable “chemical handle”for the enantioselective transformation of easily accessible fluorine-containing chemicals, such as trifluoromethyl alkenes, allylic fluorides, propargylgem-difluorides,gem-difluoroalkenes, polyfluoroarenes,dienyl fluorides, and trifluoromethyl (hetero)arenes. We aim to inspire chemists to continue their interestin both research topics of C–F bond activation and asymmetric catalysis.

Organic Chemistry Frontiers2023,10,3909-3928. (2023 Organic Chemistry Frontiers HOT articles.Impact factor: 5.4)

论文链接：https://pubs.rsc.org/en/content/articlelanding/2023/QO/D3QO00751K