Theoretical study on the mechanism of the reaction for alkene hydroaminations catalyzed by chiral aldehyde. Issue 22 (4th June 2013)

• Record Type: Journal Article
• Authors: Zhao, Jinfeng; Sun, Chuanzhi; Sun, Nan; Meng, Lin; Chen, Dezhan
• Is Part Of: International journal of quantum chemistry. Volume 113:Issue 22(2013:Nov. 15)
• Page Start: 2457
• Page End: 2463
• Publication Date: 2013-06-04
• Subjects: Quantum chemistry -- Periodicals; 541.28
• DOI: 10.1002/qua.24483
• Languages: English
• ISSNs: 0020-7608

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>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 <italic>S</italic> and <italic>R</italic> configurations. Enantioselectivity is attributed to the different forming ways of a planar five‐membered ring. The preferred pathways for the <italic>S</italic>‐configuration product (<bold>S3</bold>) and <italic>R</italic>‐configuration product (<bold>R3</bold>) are confirmed. © 2013 Wiley Periodicals, Inc.</p> </abstract>