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Iron‐Catalyzed Tertiary Alkylation of Terminal Alkynes with 1,3‐Diesters via a Functionalized Alkyl Radical
Author(s) -
Tian MingQing,
Shen ZhenYao,
Zhao Xuefei,
Walsh Patrick J.,
Hu XuHong
Publication year - 2021
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.202100641
Subject(s) - alkylation , chemistry , catalysis , bond cleavage , alkyl , selectivity , cleavage (geology) , reactivity (psychology) , heteroatom , combinatorial chemistry , stereochemistry , medicinal chemistry , organic chemistry , materials science , medicine , alternative medicine , pathology , fracture (geology) , composite material
Abstract Direct oxidative C(sp)−H/C(sp 3 )−H cross‐coupling offers an ideal and environmentally benign protocol for C(sp)−C(sp 3 ) bond formations. As such, reactivity and site‐selectivity with respect to C(sp 3 )−H bond cleavage have remained a persistent challenge. Herein is reported a simple method for iron‐catalyzed/silver‐mediated tertiary alkylation of terminal alkynes with readily available and versatile 1,3‐dicarbonyl compounds. The reaction is suitable for an array of substrates and proceeds in a highly selective manner even employing alkanes containing other tertiary, benzylic, and C(sp 3 )−H bonds alpha to heteroatoms. Elaboration of the products enables the synthesis of a series of versatile building blocks. Control experiments implicate the in situ generation of a tertiary carbon‐centered radical species.