Asymmetric Rhodium-Catalyzed Addition of Thiols to Allenes: Synthesis of Branched Allylic Thioethers and Sulfones

A highly regio‐ and enantioselective hydrothiolation of terminal allenes, a reaction which fulfills the criteria of atom economy, is reported. Applying two chiral rhodium catalyst systems, a wide variety of thiols and allenes could be coupled. Oxidation gave access to the corresponding allylic sulfo...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2015-03, Vol.54 (10), p.3121-3125
Main Authors: Pritzius, Adrian B., Breit, Bernhard
Format: Article
Language:English
Subjects:
Aliphatic compounds
asymmetric catalysis
Branched
Catalysts
Economics
enantioselectivity
ethers
rhodium
Sulfones
sulfur
Synthesis
Terminals
Thiols
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Summary:A highly regio‐ and enantioselective hydrothiolation of terminal allenes, a reaction which fulfills the criteria of atom economy, is reported. Applying two chiral rhodium catalyst systems, a wide variety of thiols and allenes could be coupled. Oxidation gave access to the corresponding allylic sulfones in essentially enantiomerically pure form. The reaction tolerates a variety of functional groups and labeling experiments gave first insights into the reaction mechanism of this new methodology. All about S: The rhodium‐catalyzed enantioselective hydrothiolation of terminal monosubstituted allenes with aromatic and functionalized aliphatic thiols permits the atom‐economic synthesis of valuable branched allylic thioethers and sulfones in high regio‐ and enantioselectivity. By varying the ligand and reaction conditions both aromatic and aliphatic thiols were tolerated.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201411402