Asymmetric Hydrogenation of Oximes Synergistically Assisted by Lewis and Brønsted Acids

Wang，Fangyuan1; Chen，Yu1; Yu，Peiyuan1; Chen，Gen Qiang2; Zhang，Xumu1

2022

10.1021/jacs.2c07506

Journal of the American Chemical Society   Impact Factor & Quartile

0002-7863

1520-5126

Due to their low reactivity, difficult enantiocontrol, and proneness to N-O bond cleavage, the catalytic asymmetric hydrogenation of oximes to hydroxylamines has remained a significant challenge. Herein, a Lewis and Brønsted acid cooperation strategy was established for the asymmetric hydrogenation of oximes, providing the corresponding hydroxylamines with up to 95% yield and up to 96% ee. Addition of Lewis and Brønsted acid was crucial to obtain high conversion and enantioselectivity. Mechanistic investigations indicates that the thiourea fragment of the ligand, Lewis acid (In(OTf)3 or Zn(OAc)2), as well as the Brønsted acid (l-CSA) played vital roles in the control of reactivity and enantioselectivity of the reaction. In addition, the synthetic elaboration of this transformation was demonstrated by gram scale experiment with retention of the yield and enantioselectivity.

SCI

English

NI Journal Papers

First ; Corresponding

National Key R&D Program of China[2021YFF0701604] ; Shenzhen Science and Technology Innovation Committee["JCYJ20210324104202007","JSGG20170821140353405"] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Guangdong Basic and Applied Basic Research Foundation[2022B1515020055] ; National Natural Science Foundation of China["21991113","21901107","22171129"]

Chemistry

Chemistry, Multidisciplinary

WOS:000869939400001

AMER CHEMICAL SOC

2-s2.0-85139187006

Scopus

1.Department of Chemistry and Shenzhen Grubbs Institute,Southern University of Science and Technology,Shenzhen,518000,China
2.Academy for Advanced Interdisciplinary Studies,Southern University of Science and Technology,Shenzhen,518000,China

Wang，Fangyuan,Chen，Yu,Yu，Peiyuan,et al. Asymmetric Hydrogenation of Oximes Synergistically Assisted by Lewis and Brønsted Acids[J]. Journal of the American Chemical Society,2022.

Wang，Fangyuan,Chen，Yu,Yu，Peiyuan,Chen，Gen Qiang,&Zhang，Xumu.(2022).Asymmetric Hydrogenation of Oximes Synergistically Assisted by Lewis and Brønsted Acids.Journal of the American Chemical Society.

Wang，Fangyuan,et al."Asymmetric Hydrogenation of Oximes Synergistically Assisted by Lewis and Brønsted Acids".Journal of the American Chemical Society (2022).