Catalyst‐Dependent Chemoselective Formal Insertion of Diazo Compounds into C−C or C−H Bonds of 1, 3‐Dicarbonyl Compounds. Issue 29 (8th May 2018)

• Record Type: Journal Article
• Authors: Liu, Zhaohong; Sivaguru, Paramasivam; Zanoni, Giuseppe; Anderson, Edward A.; Bi, Xihe
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 29(2018)
• Page Start: 8927
• Page End: 8931
• Publication Date: 2018-05-08
• Subjects: 1, 3-dicarbonyl compounds -- C−C insertion -- C−H insertion -- diazo compounds -- silver catalysis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201802834
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A catalyst‐dependent chemoselective one‐carbon insertion of diazo compounds into the C−C or C−H bonds of 1, 3‐dicarbonyl species is reported. In the presence of silver(I) triflate, diazo insertion into the C(=O)−C bond of the 1, 3‐dicarbonyl substrate leads to a 1, 4‐dicarbonyl product containing an all‐carbon α‐quaternary center. This reaction constitutes the first example of an insertion of diazo‐derived carbenoids into acyclic C−C bonds. When instead scandium(III) triflate was applied as the catalyst, the reaction pathway switched to formal C−H insertion, affording 2‐alkylated 1, 3‐dicarbonyl products. Different reaction pathways are proposed to account for this powerful catalyst‐dependent chemoselectivity. Abstract : Catalyst control : The catalyst‐dependent chemoselective insertion of diazo compounds into 1, 3‐dicarbonyl species is reported. In the presence of AgOTf, the diazo compounds selectively insert into the C(=O)−C bond, affording 1, 4‐dicarbonyl products with an all‐carbon α‐quaternary center. In contrast, in the presence of Sc(OTf)3, C−H insertion results in α‐C−H alkylation products. The cover picture for this article is presented on the back cover ofAngewandte Chemie issue 32/2018.