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Catalyst‐Dependent Chemoselective Formal Insertion of Diazo Compounds into C−C or C−H Bonds of 1,3‐Dicarbonyl Compounds
Author(s) -
Liu Zhaohong,
Sivaguru Paramasivam,
Zai Giuseppe,
Anderson Edward A.,
Bi Xihe
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201802834
Subject(s) - diazo , chemoselectivity , trifluoromethanesulfonate , chemistry , catalysis , scandium , medicinal chemistry , substrate (aquarium) , insertion reaction , alkylation , stereochemistry , combinatorial chemistry , organic chemistry , oceanography , geology
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.