Catalytic Asymmetric Functionalization of Aromatic CH Bonds by Electrophilic Trapping of Metal-Carbene-Induced Zwitterionic Intermediates

Asymmetric functionalization of aromatic CH bonds of N,N‐disubstituted anilines with diazo compounds and imines is reported for the efficient construction of α,α‐diaryl benzylic quaternary stereocenters in good yields with high diastereoselectivities and excellent enantioselectivities. This RhII/ch...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2014-11, Vol.53 (48), p.13098-13101
Main Authors: Jia, Shikun, Xing, Dong, Zhang, Dan, Hu, Wenhao
Format: Article
Language:English
Subjects:
Aniline
Aromatic compounds
asymmetric catalysis
Asymmetry
carbenes
Catalysis
Construction
CH activation
Imines
Methane - analogs & derivatives
Methane - chemistry
Models, Molecular
Molecular Structure
Phosphoric acid
rhodium
Rhodium - chemistry
Stereoisomerism
Transformations
Trapping
zwitterions
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Summary:Asymmetric functionalization of aromatic CH bonds of N,N‐disubstituted anilines with diazo compounds and imines is reported for the efficient construction of α,α‐diaryl benzylic quaternary stereocenters in good yields with high diastereoselectivities and excellent enantioselectivities. This RhII/chiral phosphoric acid cocatalyzed transformation is proposed to proceed through a metal‐carbene‐induced zwitterionic intermediate which undergoes electrophilic trapping. To the best of our knowledge, this is the first asymmetric example of metal carbene‐induced intermolecular functionalization of aryl CH bonds. Caught in a trap: The title reaction of N,N‐disubstituted anilines with diazo compounds and imines is reported for the efficient construction of α,α‐diaryl benzylic quaternary stereocenters in good yields with high diastereoselectivities and excellent enantioselectivities. Efficient electrophilic trapping of the metal‐carbene‐induced zwitterionic intermediate is crucial for the enantiocontrol under RhII/chiral phosphoric acid (PPA) co‐catalysis.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201406492