Asymmetric Three-Component Heck Arylation/Amination of Nonconjugated Cyclodienes

Daoyong Zhu; Zhiwei Jiao; Yonggui Robin Chi; Théo P Gonçalves; Kuo-Wei Huang; Jianrong Steve Zhou

doi:10.1002/anie.201915864

Asymmetric Three-Component Heck Arylation/Amination of Nonconjugated Cyclodienes

Angew Chem Int Ed Engl. 2020 Mar 23;59(13):5341-5345. doi: 10.1002/anie.201915864. Epub 2020 Feb 11.

Authors

Daoyong Zhu¹, Zhiwei Jiao¹, Yonggui Robin Chi¹, Théo P Gonçalves², Kuo-Wei Huang², Jianrong Steve Zhou³

Affiliations

¹ Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore.
² KAUST Catalysis Center and Division of Physical Science and Technology, Thuwal, 23955-6900, Saudi Arabia.
³ State Key Laboratory of Chemical Oncogenomics, Key Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Room F312, 2199 Lishui Road, Nanshan District, Shenzhen, 518055, China.

PMID: 31965664
DOI: 10.1002/anie.201915864

Abstract

Substituted cyclohexylamines are becoming increasingly important in drug discovery. Asymmetric Heck insertion/amination of nonconjugated cyclodienes proceeds to give 5-aryl cyclohexenylamines with good enantioselectivity and exclusive trans configurations. Primary and secondary anilines, indoline, and benzylamines are suitable amines. The weakly donating diphosphite Kelliphite forms a deep unsymmetrical pocket, which is essential for stereoselective anti attack of amines.

Keywords: Heck reaction; allylic amination; metal migration; palladium; phosphites.

Publication types

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