Catalytic asymmetric functionalization of aromatic C-H bonds by electrophilic trapping of metal-carbene-induced zwitterionic intermediates

Shikun Jia; Dong Xing; Dan Zhang; Wenhao Hu

doi:10.1002/anie.201406492

Catalytic asymmetric functionalization of aromatic C-H bonds by electrophilic trapping of metal-carbene-induced zwitterionic intermediates

Angew Chem Int Ed Engl. 2014 Nov 24;53(48):13098-101. doi: 10.1002/anie.201406492. Epub 2014 Sep 4.

Authors

Shikun Jia¹, Dong Xing, Dan Zhang, Wenhao Hu

Affiliation

¹ Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development; Department of Chemistry, East China Normal University, 3663, North Zhongshan Road, Shanghai, 200062 (China).

PMID: 25195569
DOI: 10.1002/anie.201406492

Abstract

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 Rh(II)/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.

Keywords: CH activation; asymmetric catalysis; carbenes; rhodium; zwitterions.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Catalysis
Methane / analogs & derivatives*
Methane / chemistry
Models, Molecular
Molecular Structure
Rhodium / chemistry*
Stereoisomerism

Substances

carbene
Rhodium
Methane