Asymmetric Alkenylation of Enones and Imines Enabled by A Highly Efficient Aryl to Vinyl 1,4-Rhodium Migration

Shu-Sheng Zhang; Tian-Jiao Hu; Meng-Yao Li; Yi-Kang Song; Xiao-Di Yang; Chen-Guo Feng; Guo-Qiang Lin

doi:10.1002/anie.201813585

Asymmetric Alkenylation of Enones and Imines Enabled by A Highly Efficient Aryl to Vinyl 1,4-Rhodium Migration

Angew Chem Int Ed Engl. 2019 Mar 11;58(11):3387-3391. doi: 10.1002/anie.201813585. Epub 2019 Feb 4.

Authors

Shu-Sheng Zhang¹, Tian-Jiao Hu², Meng-Yao Li², Yi-Kang Song¹, Xiao-Di Yang¹, Chen-Guo Feng^{1

2}, Guo-Qiang Lin^{1

2}

Affiliations

¹ Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai, 201203, China.
² Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, 200032, China.

PMID: 30644152
DOI: 10.1002/anie.201813585

Abstract

The asymmetric rhodium-catalyzed alkenylation of enones and imines with arylboronic acids has been developed. A highly controllable aryl to vinyl 1,4-rhodium migration is the key step. Stereodefined vinyl moieties were installed in excellent enantioselectivies for most examined examples. DFT calculations reveal that the driving force of this rhodium migration is a kinetically favored process.

Keywords: C−H functionalization; alkenylation; asymmetric catalysis; metal migration; rhodium.

Publication types

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

Abstract

Publication types

Grants and funding