Chiral Atropisomeric‐NHC Catechodithiolate Ruthenium Complexes for Z‐Selective Asymmetric Ring‐Opening Cross Metathesis of Exo‐Norbornenes

A set of 16 chiral ruthenium complexes containing atropisomerically stable N‐Heterocyclic Carbene (NHC) ligands was synthesized from prochiral NHC precursors. After a rapid screening in asymmetric ring‐opening‐cross metathesis (AROCM), the most effective chiral atropBIAN‐NHC Ru‐catalyst (up to 97 : ...

Full description

Saved in:
Bibliographic Details
Published in:Chemistry : a European journal 2023-05, Vol.29 (28), p.e202300341-n/a
Main Authors: Morvan, Jennifer, Bouëtard, Dylan, Kong, Lingyu, Chou, Yajie, Vives, Thomas, Albalat, Muriel, Roisnel, Thierry, Crévisy, Christophe, Nava, Paola, Humbel, Stéphane, Vanthuyne, Nicolas, Clavier, Hervé, Mauduit, Marc
Format: Article
Language:English
Subjects:
Asymmetry
atropisomers
Catalysts
Chemical Sciences
Chemistry
Enantiomers
enantioselectivity
Metathesis
NHC
olefin metathesis
Ruthenium
Ruthenium compounds
Z-selectivity
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:A set of 16 chiral ruthenium complexes containing atropisomerically stable N‐Heterocyclic Carbene (NHC) ligands was synthesized from prochiral NHC precursors. After a rapid screening in asymmetric ring‐opening‐cross metathesis (AROCM), the most effective chiral atropBIAN‐NHC Ru‐catalyst (up to 97 : 3 er) was then converted to a Z‐selective catechodithiolate complex. The latter proved to be highly efficient in Z‐selective AROCM of exo‐norbornenes affording valuable trans‐cyclopentanes with excellent Z‐selectivity (>98 %) and high enantioselectivity (up to 96.5 : 3.5 er). A set of 16 chiral ruthenium complexes containing atropisomerically stable NHCs was synthesized in good yields with excellent enantiomeric purities (up >99.75 : 0.25 er). The chiral BIAN‐based Ru‐complexes Ru‐4 g was the most efficient to catalyse the AROCM of endo‐ and exo‐norbornenes (up to 97 : 3 er). Successfully converted into its corresponding Z‐selective catechodithiolate complex Z‐Ru‐5, the latter demonstrated high efficiency in Z‐selective AROCM of exo‐norbornenes affording valuable trans‐cyclopentanes in >98 % Z‐selectivity and the highest enantioselectivities reported so far (up to 96.5 : 3.5 er).
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202300341