Get access
Advertisement

Theoretical study on the mechanism of the reaction for alkene hydroaminations catalyzed by chiral aldehyde

Authors

  • Jinfeng Zhao,

    1. Department of Chemistry, College of Chemistry, Chemical Engineering, and Materials Science, Shandong Normal University, Jinan, People's Republic of ChinaFax: (+86) 531 861 80304.
    Search for more papers by this author
  • Chuanzhi Sun,

    Corresponding author
    • Department of Chemistry, College of Chemistry, Chemical Engineering, and Materials Science, Shandong Normal University, Jinan, People's Republic of ChinaFax: (+86) 531 861 80304.
    Search for more papers by this author
  • Nan Sun,

    1. Department of Chemistry, College of Chemistry, Chemical Engineering, and Materials Science, Shandong Normal University, Jinan, People's Republic of ChinaFax: (+86) 531 861 80304.
    Search for more papers by this author
  • Lin Meng,

    1. Department of Chemistry, College of Chemistry, Chemical Engineering, and Materials Science, Shandong Normal University, Jinan, People's Republic of ChinaFax: (+86) 531 861 80304.
    Search for more papers by this author
  • Dezhan Chen

    Corresponding author
    • Department of Chemistry, College of Chemistry, Chemical Engineering, and Materials Science, Shandong Normal University, Jinan, People's Republic of ChinaFax: (+86) 531 861 80304.
    Search for more papers by this author

E-mail: suncz@sdnu.edu.cn or chendzh@sdnu.edu.cn

Abstract

Alkene hydroamination catalyzed by chiral aldehyde relying only on temporary intramolecularity is a new concept reaction. In this article, the reaction mechanism was investigated using density functional theory. The calculation results show that: (1) The reaction can be divided into two parts. The first part is a dehydration process involving a hemiaminal formation. The nitrone catalyst forms through rapid intermolecular nucleophilic addition of benzylhydroxylamine to chiral aldehyde precatalyst. The second part is a catalytic cycle, which involves an aminal formation—hydroamination—ring opening—product release process. (2) There are four enantioselective pathways related to the products of S and R configurations. Enantioselectivity is attributed to the different forming ways of a planar five-membered ring. The preferred pathways for the S-configuration product (S3) and R-configuration product (R3) are confirmed. © 2013 Wiley Periodicals, Inc.

Get access to the full text of this article

Ancillary