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Radical trifluoromethylation of Ti ate enolate: possible intervention of transformation of Ti(IV) to Ti(III) for radical termination
Institution:1. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk 630090, Russia;2. Karlsruhe Institute of Technology, Institute of Solid State Physics, Karlsruhe D-76344, Germany;1. Institute of Problems of Chemical Physics RAS, Chernogolovka, Russia;2. Institute of Solid State Physics RAS, Chernogolovka, Moscow Region, 142432, Russia;1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto, 606-8502, Japan;2. School of Chemical Engineering and Light Industry, Gaungdong University of Technology, No. 100, West Waihuan Road, HEMC, 4 Panyu District, Guangzhou, 510006, China
Abstract:The radical trifluoromethylation of ketone Ti ate enolates gave α-CF3 ketones in good yields. The use of excess amount of LDA and Ti(OiPr)4 in the preparation of Ti ate enolates is the key to the efficient radical trifluoromethylation. Theoretical studies on the spin density of the Ti(IV) ate ketyl radical intermediate suggest the involvement of transformation from Ti(IV) ate ketyl radical intermediates to Ti(III) species in a radical termination step.
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