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Helical Chiral N‐Heterocyclic Carbene Ligands in Enantioselective Gold Catalysis
Author(s) -
Pallova Lenka,
Abella Laura,
Jean Marion,
Vanthuyne Nicolas,
Barthes Cécile,
Vendier Laure,
Autschbach Jochen,
Crassous Jeanne,
Bastin Stéphanie,
César Vincent
Publication year - 2022
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.202200166
Subject(s) - enantioselective synthesis , helicene , cycloisomerization , chirality (physics) , chemistry , enantiomer , stereochemistry , carbene , substituent , axial chirality , combinatorial chemistry , catalysis , enantiomeric excess , ligand (biochemistry) , organic chemistry , molecule , biochemistry , chiral symmetry breaking , physics , receptor , quantum mechanics , nambu–jona lasinio model , quark
The first chiral helicene‐NHC gold(I) complexes efficient in enantioselective catalysis were prepared. The L‐shaped chiral ligand is composed of an imidazo[1,5‐ a ]pyridin‐3‐ylidene (IPy) scaffold laterally substituted by a configurationally stable [5]‐helicenoid unit. The chiral information was introduced in a key post‐functionalization step of a NHC‐gold(I) complex bearing a symmetrical anionic fluoreno[5]helicene substituent, leading to a racemic mixture of complexes featuring three correlated elements of chirality, namely central, axial and helical chirality. After HPLC enantiomeric resolution, X‐ray crystallography and theoretical calculations enabled structural and stereochemical characterization of these configurationally stable NHC‐gold(I) complexes. The high potential in asymmetric catalysis is demonstrated in the benchmark cycloisomerization of N‐tethered 1,6‐enynes with up to 95 : 5 er.