Room-temperature enantioselective C–H iodination via kinetic resolution

Asymmetric carbon-hydrogen (C–H) activation reactions often rely on desymmetrization of prochiral C–H bonds on the same achiral molecule, using a chiral catalyst. Here, we report a kinetic resolution via palladium-catalyzed enantioselective C–H iodination in which one of the enantiomers of a racemic...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2014-10, Vol.346 (6208), p.451-455
Main Authors: Chu, Ling, Xiao, Kai-Jiong, Yu, Jin-Quan
Format: Article
Language:English
Subjects:
Aromatic compounds
Asymmetry
Carbon
Catalysis
Catalysts
Chemical bonds
Enantiomers
Enzyme kinetics
Hydrogen bonds
Iodination
Kinetics
Organic Chemistry
Palladium
Proteins
Reaction kinetics
Substrates
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Summary:Asymmetric carbon-hydrogen (C–H) activation reactions often rely on desymmetrization of prochiral C–H bonds on the same achiral molecule, using a chiral catalyst. Here, we report a kinetic resolution via palladium-catalyzed enantioselective C–H iodination in which one of the enantiomers of a racemic benzylic amine substrates undergoes faster aryl C–H insertion with the chiral catalysts than the other. The resulting enantioenriched C–H functionalization products would not be accessible through desymmetrization of prochiral C–H bonds. The exceedingly high relative rate ratio (k fast/k slow up to 244), coupled with the subsequent iodination of the remaining enantiomerically enriched starting material using a chiral ligand with the opposite configuration, enables conversion of both substrate enantiomers into enantiomerically pure iodinated products.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.1258538