Theoretical study on the mechanism of the reaction for alkene hydroaminations catalyzed by chiral aldehyde
Article first published online: 4 JUN 2013
Copyright © 2013 Wiley Periodicals, Inc.
International Journal of Quantum Chemistry
Volume 113, Issue 22, pages 2457–2463, 15 November 2013
How to Cite
How to cite this article: Int. J. Quantum Chem. 2013, 113, 2457–2463. DOI: 10.1002/qua.24483, , , , ,
- Issue published online: 7 OCT 2013
- Article first published online: 4 JUN 2013
- Manuscript Accepted: 8 MAY 2013
- Manuscript Revised: 6 MAY 2013
- Manuscript Received: 24 FEB 2013
- National Natural Science Foundations of China. Grant Number: 20975064
- Advanced School Program of Science and Technology of Shandong Province. Grant Number: J12LD09
- chiral aldehyde · alkene hydroamination · temporary tether · reverse cope elimination · density functional theory
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.