Premium
Generation of Reactive Species by One‐Electron Reduction of Fischer‐Type Carbene Complexes of Group 6 Metals and Their Use for Carbon–Carbon Bond Formation
Author(s) -
Fuchibe Kohei,
Iwasawa Nobuharu
Publication year - 2003
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.200390112
Subject(s) - carbene , carbon fibers , chemistry , group (periodic table) , reduction (mathematics) , materials science , organic chemistry , catalysis , composite number , mathematics , composite material , geometry
Carbon–carbon bond‐forming reactions mediated by one‐electron reduction of Fischer‐type carbene complexes of Group 6 metals were investigated. In the case of aryl‐ or silylcarbene complexes of tungsten, the anion radical species generated by one‐electron reduction smoothly underwent addition reaction to ethyl acrylate. One‐electron reduction of α , β ‐unsaturated carbene complexes afforded biscarbene complexes by dimerization of the corresponding anion radical species at the position γ to the metal center. In contrast, one‐electron reduction of chromium phenyl‐ or alkylcarbene complexes gave, via carbonyl insertion, α ‐methoxyacylchromate complexes, which further underwent conjugate addition to various electron‐poor olefins to give the corresponding α ‐methoxyketones.