- Direct C(sp3)?H Trifluoromethylation of Unactivated Alkanes Enabled by Multifunctional Trifluoromethyl Copper Complexes
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A mild and operationally simple C(sp3)?H trifluoromethylation method was developed for unactivated alkanes by utilizing a bench-stable CuIII complex, bpyCu(CF3)3, as the initiator of the visible-light photoinduced reaction, the source of a trifluoromethyl radical as a hydrogen atom transfer reagent, and the source of a trifluoromethyl anion for functionalization. The reaction was initiated by the generation of reactive electrophilic carbon-centered CF3 radical through photoinduced homolytic cleavage of bpyCu(CF3)3, followed by hydrogen abstraction from an unactivated C(sp3)?H bond. Comprehensive mechanistic investigations based on a combination of experimental and computational methods suggested that C?CF3 bond formation was enabled by radical–polar crossover and ionic coupling between the resulting carbocation intermediate and the anionic CF3 source. The methylene-selective reaction can be applied to the direct, late-stage trifluoromethylation of natural products and bioactive molecules.
- Choi, Geunho,Lee, Geun Seok,Park, Beomsoon,Kim, Dongwook,Hong, Soon Hyeok
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supporting information
p. 5467 - 5474
(2021/01/20)
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- Csp3-H Trifluoromethylation of Unactivated Aliphatic Systems
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A straightforward method for the undirected trifluoromethylation of unactivated methylene units was developed. The reaction proceeds in aqueous acetonitrile with Grushin's reagent, bpyCu(CF3)3, under broad-spectrum white-light irradiation. The trifluoromethylation tolerates a wide range of functional groups including ketones, esters, nitriles, amides, alcohols, and carboxylic acids. The C-H cleavage step is performed via intermolecular H atom abstraction, and the selectivities across a range of methylene units are reported. Mechanistic studies offer a general reaction coordinate for the overall transformation.
- He, Jiachen,Nguyen, Truong N.,Guo, Shuo,Cook, Silas P.
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supporting information
p. 702 - 705
(2021/02/01)
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- Catalytic asymmetric hydrogenation of α-CF3- or β-CF3-Substituted acrylic acids using Rhodium(I) complexes with a combination of chiral and achiral ligands
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Only the mixture works! Acrylic acid derivatives with CF3 substituents in α or β position were efficiently hydrogenated in the presence of a RhI complex with a chiral secondary phosphine oxide (SPO; see scheme) and an achiral Ph3P as ligands. The corresponding propanoic acid derivatives were obtained with generally high conversion (>99 %) and high enantioselectivity (92->99 %). Copyright
- Dong, Kaiwu,Li, Yang,Wang, Zheng,Ding, Kuiling
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supporting information
p. 14191 - 14195
(2014/01/06)
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- Process for producing optically active carboxylic acid
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A process for the production of an optically active carboxylic acid (I), which comprises subjecting an olefinic carboxylic acid (II) to asymmetric hydrogenation using a complex as a catalyst consisting of an optically active phosphine (III) and a ruthenium compound. Complex of STR1 with a ruthenium compound STR2 According to the process of the present invention, optically active carboxylic acids can be produced with high yield.
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