Catalytic Asymmetric Radical-Polar Crossover Hydroalkoxylation

被引：108

作者：

Discolo, Christopher A. ^{[1
]}

Touney, Eric E. ^{[1
]}

Pronin, Sergey V. ^{[1
]}

机构：

[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2019年 / 141卷 / 44期

关键词：

BOND-DISSOCIATION ENERGIES; COBALT-CARBON BONDS; UNACTIVATED ALKENES; OLEFIN HYDROAMINATION; ELECTRONIC-STRUCTURE; PI INTERACTIONS; COMPLEXES; MECHANISM; FE; HYDROGENATION;

D O I：

10.1021/jacs.9b10645

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Asymmetric intramolecular hydrofunctionalization of tertiary allylic alcohols is described. This metal hydride-mediated catalytic radical-polar crossover reaction delivers corresponding epoxides in good to high enantioselectivity and constitutes the first example of asymmetric hydrogen atom transfer-initiated process. A series of modified cobalt salen complexes has proven optimal for achieving good efficiency and asymmetric induction. Experimental data suggest that cationic cobalt complexes may be involved in the enantiodetermining step, where cation-pi interactions in the catalyst contribute to the asymmetric induction.

引用

页码：17527 / 17532

页数：6

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