Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Three-Component Radical-Initiated 1,2-Dicarbofunctionalization of Alkenes

Lin, Jin-Shun1,2; Li, Tao-Tao1,2; Liu, Ji-Ren4; Jiao, Guan-Yuan1,2; Gu, Qiang-Shuai3; Cheng, Jiang-Tao1,2; Guo, Yu-Long1,2; Hong, Xin4; Liu, Xin-Yuan1,2

2019-01-16

10.1021/jacs.8b11736

Journal of the American Chemical Society   影响因子和分区

0002-7863

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.

SCI ; EI ; IC ; CCR

英语

NI期刊

第一 ; 通讯

Shenzhen Nobel Prize Scientists Laboratory Project[C17213101]

Chemistry

Chemistry, Multidisciplinary

WOS:000456350300049

AMER CHEMICAL SOC

20190206360650

Biochemistry ; Carbon ; Catalysis ; Copper compounds ; Enantioselectivity ; Hydrogen bonds ; Phosphoric acid ; Reaction intermediates

Biochemistry:801.2 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2 ; Probability Theory:922.1

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol, SUSTech Acad Adv Interdisciplinary Studies, Shenzhen 518055, Peoples R China
4.Zhejiang Univ, Dept Chem, Hangzhou 310027, Zhejiang, Peoples R China

Lin, Jin-Shun,Li, Tao-Tao,Liu, Ji-Ren,et al. Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Three-Component Radical-Initiated 1,2-Dicarbofunctionalization of Alkenes[J]. Journal of the American Chemical Society,2019,141(2):1074-1083.

Lin, Jin-Shun.,Li, Tao-Tao.,Liu, Ji-Ren.,Jiao, Guan-Yuan.,Gu, Qiang-Shuai.,...&Liu, Xin-Yuan.(2019).Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Three-Component Radical-Initiated 1,2-Dicarbofunctionalization of Alkenes.Journal of the American Chemical Society,141(2),1074-1083.

Lin, Jin-Shun,et al."Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Three-Component Radical-Initiated 1,2-Dicarbofunctionalization of Alkenes".Journal of the American Chemical Society 141.2(2019):1074-1083.