Helical Chiral N‐Heterocyclic Carbene Ligands in Enantioselective Gold Catalysis
Abstract 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 informatio...
Published in: | Chemistry – A European Journal |
---|---|
Main Authors: | , , , , , , , , , |
Other Authors: | , |
Format: | Article in Journal/Newspaper |
Language: | English |
Published: |
Wiley
2022
|
Subjects: | |
Online Access: | http://dx.doi.org/10.1002/chem.202200166 https://onlinelibrary.wiley.com/doi/pdf/10.1002/chem.202200166 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.202200166 https://chemistry-europe.onlinelibrary.wiley.com/doi/am-pdf/10.1002/chem.202200166 |
Summary: | Abstract 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. |
---|