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Indolizy Carbene Ligand. Evaluation of Electronic Properties and Applications in Asymmetric Gold(I) Catalysis
Author(s) -
Martinez Thibaut,
Vanitcha Avassaya,
Troufflard Claire,
Vanthuyne Nicolas,
Forté Jérémy,
Gontard Geoffrey,
Lemière Gilles,
MourièsMansuy Virginie,
Fensterbank Louis
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.202106142
Subject(s) - carbene , moiety , chemistry , stereocenter , methylene , phosphine , enantioselective synthesis , bifunctional , catalysis , ligand (biochemistry) , combinatorial chemistry , phosphine oxide , stereochemistry , medicinal chemistry , organic chemistry , biochemistry , receptor
We report herein a new family of carbene ligands based on an indolizine‐ylidene (Indolizy) moiety. The corresponding gold(I) complexes are easily obtained from the gold(I)‐promoted cyclization of allenylpyridine precursors. Evaluation of the electronic properties by experimental methods and also by DFT calculations confirms strong σ‐donating and π‐accepting properties of these ligands. Cationization of the gold(I) complexes generates catalytic species that trigger diverse reactions of (poly)unsaturated precursors. When armed with a methylene phosphine oxide moiety on the stereogenic center adjacent to the nitrogen atom, the corresponding bifunctional carbene ligands give rise to highly enantioselective heterocyclizations. DFT calculations brought some rationalization and highlighted the critical roles played by the phosphine oxide group and the tosylate anion in the asymmetric cyclization of γ‐allenols.