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Metal‐Free Direct Alkylation of Ketene Dithioacetals by Oxidative C(sp 2 )−H/C(sp 3 )−H Cross‐Coupling
Author(s) -
Wen Jiangwei,
Zhang Fan,
Shi Wenyan,
Lei Aiwen
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701664
Subject(s) - ketene , alkylation , olefin fiber , chemistry , bond cleavage , metal , oxidative phosphorylation , cleavage (geology) , oxidative cleavage , oxidative coupling of methane , functional group , medicinal chemistry , stereochemistry , organic chemistry , catalysis , materials science , biochemistry , fracture (geology) , composite material , polymer
The functionalization of internal olefins has been a challenging task in organic synthesis. This protocol provides an efficient and transition‐metal‐free direct oxidative C(sp 2 )−H/C(sp 3 )−H cross‐coupling method to access tetrasubstituted olefins. The push–pull effect from the polarized olefin substrates accelerates the internal olefin C−H alkylation. Importantly, the mechanistic experimental results demonstrate that the alkanes C−H bond cleavage is the rate‐determining step, and a radical pathway has been proposed for the alkylation reaction. Notably, the present protocol has excellent functional group tolerance and could be easily scaled up with good efficiency.