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C 2 ‐Symmetric Chiral Disulfoxide Ligands in Rhodium‐Catalyzed 1,4‐Addition: From Ligand Synthesis to the Enantioselection Pathway
Author(s) -
Mariz Ronaldo,
Poater Albert,
Gatti Michele,
Drinkel Emma,
Bürgi Justus J.,
Luan Xinjun,
Blumentritt Sascha,
Linden Anthony,
Cavallo Luigi,
Dorta Reto
Publication year - 2010
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.201001749
Subject(s) - rhodium , phenylboronic acid , catalysis , ligand (biochemistry) , chemistry , catalytic cycle , asymmetric induction , stereochemistry , density functional theory , combinatorial chemistry , enantioselective synthesis , computational chemistry , organic chemistry , receptor , biochemistry
A family of chiral C 2 ‐symmetric disulfoxide ligands possessing biaryl atropisomeric backbones has been synthesized by using the Andersen methodology. Complete characterization includes X‐ray crystallographic studies of all ligands and some of their rhodium complexes. Their synthesis, optical purity, electronic properties, and catalytic behavior in the prototypical rhodium‐catalyzed 1,4‐addition of phenylboronic acid to 2‐cyclohexen‐1‐one are presented through an in depth study of this ligand class. Density functional theory calculations on the step of the catalytic cycle that determines the enantioselectivity are presented and reinforce the first hypothetical explanations for the high levels of asymmetric induction observed.