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- W2897699124 abstract "The mechanism of the aryl iodide-catalyzed asymmetric migratory geminal difluorination of β-substituted styrenes (Banik et al. Science 2016, 353, 51) has been explored with density functional theory computations. The computed mechanism consists of (a) activation of iodoarene difluoride (ArIF2), (b) enantiodetermining 1,2-fluoroiodination, (c) bridging phenonium ion formation via SN2 reductive displacement, and (d) regioselective fluoride addition. According to the computational model, the ArIF2 intermediate is stabilized through halogen−π interactions between the electron-deficient iodine(III) center and the benzylic substituents at the catalyst stereogenic centers. Interactions with the catalyst ester carbonyl groups (I(III)+···O) are not observed in the unactivated complex, but do occur upon activation of ArIF2 through hydrogen-bonding interactions with external Brønsted acid (HF). The 1,2-fluoroiodination occurs via alkene complexation to the electrophilic, cationic I(III) center followed by C–F bond formation anti to the forming C–I bond. The bound olefin and the C–I bond of catalyst adopt a spiro arrangement in the favored transition structures but a nearly periplanar arrangement in the disfavored transition structures. Multiple attractive non-covalent interactions, including slipped π···π stacking, C–H···O, and C–H···π interactions, are found to underlie the high asymmetric induction. The chemoselectivity for 1,1-difluorination versus 1,2-difluorination is controlled mainly by (1) the steric effect of the substituent on the olefinic double bond and (2) the nucleophilicity of the carbonyl oxygen of substrate." @default.
- W2897699124 created "2018-10-26" @default.
- W2897699124 creator A5028260842 @default.
- W2897699124 creator A5030701079 @default.
- W2897699124 creator A5037736695 @default.
- W2897699124 creator A5042178740 @default.
- W2897699124 creator A5058629788 @default.
- W2897699124 date "2018-10-23" @default.
- W2897699124 modified "2023-10-10" @default.
- W2897699124 title "Mechanism and Origins of Chemo- and Stereoselectivities of Aryl Iodide-Catalyzed Asymmetric Difluorinations of β-Substituted Styrenes" @default.
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