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oai:figshare.com:article/34027560 2026-09-29T20:09:28Z category_1 category_4 category_12 category_13 category_14 category_24 category_272 category_873 category_135 portal_63 item_type_6 month_year_09_2026

Copper-Catalyzed Strain-Driven Enantiospecific C–C Oxidative Addition Zhong-Tao Jiang (1924084) Yuanyue Zhao (25138821) Tonglin Zhao (21334943) Mingyue Deng (19442727) Yu Lan (132241) Li-Li Liao (4232515) Ying Xia (222301) Biophysics Biochemistry Cell Biology Genetics Molecular Biology Evolutionary Biology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Computational Biology furnishes branched fluoroallylamines concerted reductive elimination new mechanistic framework new elementary step new strategies remained elusive oxidative addition gem </ findings reveal enantiospecific cross combined experimental analogous transformations allylation chemistry >- difluorocyclopropanes While oxidative addition for C–C bond cleavage has been established using noble metals such as palladium and rhodium, analogous transformations with copper have remained elusive. Herein, we report a copper-catalyzed, enantiospecific cross-coupling of <i>gem</i>-difluorocyclopropanes with anilines that furnishes branched fluoroallylamines. Combined experimental and computational studies provide compelling evidence for the oxidative addition of a C–C bond to copper, thereby establishing a new elementary step in copper catalysis. Moreover, our findings reveal an unusual concerted substitution type reductive elimination for C–N bond formation that involves simultaneous C–F and N–H bond cleavage, bypassing conventional allylic metal intermediates and establishing a new mechanistic framework for allylation chemistry. The mechanistic principles demonstrated herein, including the pivotal C–C oxidative addition to copper and the concerted reductive elimination, pave the way for new strategies in catalytic C–C bond functionalization. 2026-09-29T00:00:00Z Text Journal contribution 10.1021/jacs.6c14022.s001 https://figshare.com/articles/journal_contribution/Copper-Catalyzed_Strain-Driven_Enantiospecific_C_C_Oxidative_Addition/34027560 CC BY-NC 4.0