C2-Symmetric Chiral Disulfoxide Ligands in Rhodium-Catalyzed 1,4-Addition: From Ligand Synthesis to the Enantioselection Pathway

A family of chiral C2‐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,...

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Bibliographic Details
Published in:Chemistry : a European journal 2010-12, Vol.16 (48), p.14335-14347
Main Authors: Mariz, Ronaldo, Poater, Albert, Gatti, Michele, Drinkel, Emma, Bürgi, Justus J., Luan, Xinjun, Blumentritt, Sascha, Linden, Anthony, Cavallo, Luigi, Dorta, Reto
Format: Article
Language:English
Subjects:
asymmetric catalysis
Asymmetry
Boronic Acids - chemistry
Carbon - chemistry
Catalysis
Catalysts
Chemistry
chiral auxiliaries
conjugate addition
Crystallography, X-Ray
Cyclohexanones - chemical synthesis
Cyclohexanones - chemistry
Density functional theory
enantioselectivity
Ligands
Mathematical analysis
Molecular Conformation
Molecular Structure
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Rhodium
Rhodium - chemistry
Spectrophotometry, Infrared
Stereoisomerism
sulfoxides
Sulfoxides - chemical synthesis
Sulfoxides - chemistry
Synthesis
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Summary:A family of chiral C2‐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. SO selective! Chiral C2‐symmetric disulfoxide ligands that possess biaryl atropisomeric backbones are synthesized by the Andersen methodology (see picture). 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.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201001749