Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Three-Component Radical-Initiated 1,2-Dicarbofunctionalization of Alkenes
Autor: | Tao-Tao Li, Xin-Yuan Liu, Qiang-Shuai Gu, Jin-Shun Lin, Yu-Long Guo, Xin Hong, Ji-Ren Liu, Guan-Yuan Jiao, Jiang-Tao Cheng |
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Rok vydání: | 2018 |
Předmět: |
Steric effects
Enantioselective synthesis General Chemistry Carbocation 010402 general chemistry Phosphate 01 natural sciences Biochemistry Asymmetric induction Combinatorial chemistry Catalysis 0104 chemical sciences Stereocenter chemistry.chemical_compound Colloid and Surface Chemistry chemistry Phosphoric acid |
Zdroj: | Journal of the American Chemical Society. 141:1074-1083 |
ISSN: | 1520-5126 0002-7863 |
Popis: | An asymmetric intermolecular, three-component radical-initiated dicarbofunctionalization of 1,1-diarylalkenes with diverse carbon-centered radical precursors and electron-rich heteroaromatics by a copper(I) and chiral phosphoric acid cooperative catalysis strategy has been developed, providing straightforward access to chiral triarylmethanes bearing quaternary all-carbon stereocenters with high efficiency as well as excellent chemo- and enantioselectivity. The key to success is not only the introduction of a sterically demanding chiral phosphoric acid to favor radical difunctionalization over the otherwise remarkable side reactions but also the in situ generation of carbocation intermediates from benzylic radical to realize asymmetric induction with the aid of a removable hydroxy directing group via cooperative interactions with chiral phosphate. Density functional theory calculations elucidated the critical chiral environment created by the hydrogen-bonding and ion-pair interactions between the chiral phosphoric acid catalyst and substrates, which leads to the enantioselective C-C bond formation. |
Databáze: | OpenAIRE |
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