Copper-Catalyzed Intermolecular [4 + 2] Annulation Enabled by Internal Oxidant-Promoted C(sp<sup>3</sup>)–H Functionalization: Access to 3‑Trifluoromethylated 3‑Hydroxy-cyclohexan-1-ones Chuanle Zhu Hao Zeng Chi Liu Fulin Chen Huanfeng Jiang 10.1021/acs.orglett.9b01817.s001 https://acs.figshare.com/articles/journal_contribution/Copper-Catalyzed_Intermolecular_4_2_Annulation_Enabled_by_Internal_Oxidant-Promoted_C_sp_sup_3_sup_H_Functionalization_Access_to_3_Trifluoromethylated_3_Hydroxy-cyclohexan-1-ones/8263775 A copper-catalyzed diastereoselective [4 + 2] cyclolization of α,β-unsaturated ketoxime acetates and trifluoromethyl ketones affords various 3-trifluoromethylated 3-hydroxy-cylcohexan-1-ones smoothly. This reaction features the selective functionalization of a less acidic C­(sp<sup>3</sup>)–H bond by an internal oxdative C­(sp<sup>3</sup>)–H functionalization strategy. Preliminary investigations revealed that α,β-unsaturated ketoxime acetates were an internal oxidant, and the <i>in situ</i> generated H<sub>2</sub>O served as the O-source of the carbonyl oxygen in the product. 2019-06-12 14:46:47 diastereoselective carbonyl 3- trifluoromethylated 3- hydroxy-cylcohexan -1-ones Annulation Access Internal Hydroxy-cyclohexan Functionalization Trifluoromethylated Copper-Catalyzed ketone strategy investigation functionalization acidic Oxidant-Promoted O-source H 2 O Preliminary Enabled oxidant cyclolization copper-catalyzed oxdative ketoxime acetates Intermolecular bond