Rhodium(II)-Catalyzed Enantioselective Intermolecular Aziridination of Alkenes

被引：30

作者：

Boquet, Vincent ^{[1
]}

Nasrallah, Ali ^{[1
]}

Dana, Alejandro L. ^{[2
,3
]}

Brunard, Erwan ^{[1
]}

Di Chenna, Pablo H. ^{[2
,3
]}

Duran, Fernando J. ^{[2
,3
]}

Retailleau, Pascal ^{[1
]}

Darses, Benjamin ^{[5
]}

Sircoglou, Marie ^{[4
]}

Dauban, Philippe ^{[1
]}

机构：

[1] Univ Paris Saclay, Inst Chim Subst Nat, CNRS, UPR 2301, F-91198 Gif Sur Yvette, France

[2] Univ Buenos Aires, CONICET, UMYMFOR, C1428EGA, Buenos Aires, Argentina

[3] Univ Buenos Aires, Fac Ciencias Exactas & Nat, Dept Quim Organ, C1428EGA, Buenos Aires, Argentina

[4] CNRS, Inst Chim Mol & Mat Orsay, F-91405 Orsay, France

[5] Univ Grenoble Alpes, CNRS, DCM, F-38000 Grenoble, France

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2022年 / 144卷 / 37期

关键词：

C-H AMINATION; TRISUBSTITUTED AZIRIDINES; CHIRAL CATALYSTS; COPPER-COMPLEXES; DIRHODIUM(II); BONDS; SULFONAMIDES; SELECTIVITY; MECHANISM; CARBENE;

D O I：

10.1021/jacs.2c07337

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

C4-Symmetrical dirhodium(II) tetracarboxylates are highly efficient catalysts for the asymmetric intermolecular aziridination of substituted alkenes with sulfamates. The reaction proceeds with high levels of efficiency and chemoselectivity to afford aziridines with excellent yields of up to 95% and enantiomeric excesses of up to 99%. The scope of the alkene aziridination includes mono-, di-, and trisubstituted olefins as well as the late-stage functionalization of complex substrates. The reaction can be performed on a gram-scale with a catalyst loading of 0.1 mol %. Our DFT study led us to propose a two-spin-state mechanism, involving a triplet Rh-nitrene species as key intermediate to drive the stereocontrolled approach and activation of the substrate.

引用

页码：17156 / 17164

页数：9

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