Issue 14, 2018

Diastereoselectivity in a cyclic secondary amine catalyzed asymmetric Mannich reaction: a model rationalization from DFT studies

Abstract

A variation in diastereoselectivity is rationalized for cyclic secondary amine catalyzed asymmetric Mannich reactions, by systematic DFT studies on a series of representative catalysis systems. Computational results well explain the experimentally observed stereoselectivities for all the systems. Structural factors that influence the stereoselectivity are elucidated based on transition state analysis. Three structural parameters including two lengths L1 and L2, and a dihedral angle D1 of intermediates are found to be able to concisely correlate the relationship between structures and diastereoselectivities. A quantitative structure-stereoselectivity relationship (QSSR) model containing these three parameters is proposed to correlate the diastereoselectivity of Mannich reactions catalyzed by cyclic secondary amines. The model rationalization study could serve as an interesting example to understand the stereoselectivities and to advance catalyst design in asymmetric organocatalysis.

Graphical abstract: Diastereoselectivity in a cyclic secondary amine catalyzed asymmetric Mannich reaction: a model rationalization from DFT studies

Supplementary files

Article information

Article type
Research Article
Submitted
26 4 2018
Accepted
22 5 2018
First published
24 5 2018

Org. Chem. Front., 2018,5, 2148-2157

Diastereoselectivity in a cyclic secondary amine catalyzed asymmetric Mannich reaction: a model rationalization from DFT studies

S. Shu, Z. Liu, Y. Li, Z. Ke and Y. Liu, Org. Chem. Front., 2018, 5, 2148 DOI: 10.1039/C8QO00424B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements