CC BY ND NC 4.0 · SynOpen 2018; 02(02): 0122-0127
DOI: 10.1055/s-0036-1591999
paper
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Diastereoselectivity in the Aza-Michael Reaction of Chiral α-Methylbenzylamines with α,β-Unsaturated Carbonyl Compounds

M. Kour
Department of chemistry, The IIS University, GurukulMarg, SFS, Mansarovar, Jaipur 302020, India   Email: bansal56@gmail.com
,
R. Gupta
Department of chemistry, The IIS University, GurukulMarg, SFS, Mansarovar, Jaipur 302020, India   Email: bansal56@gmail.com
,
R. Saini
Central Drug Research Institute, Sitapur Road, Lucknow 226031, India
,
R. K. Bansal*
Department of chemistry, The IIS University, GurukulMarg, SFS, Mansarovar, Jaipur 302020, India   Email: bansal56@gmail.com
› Author Affiliations
Further Information

Publication History

Received: 15 March 2018

Accepted after revision: 05 April 2018

Publication Date:
07 May 2018 (online)

Abstract

The aza-Michael reaction of (S)-(–)- and (R)-(+)-α-methylbenzylamines with trans-cinnamaldehyde and other α,β-unsaturated carbonyl compounds occurs with 52–98% diastereoselectivity (de); however, in the reaction with crotonaldehyde, the de is lower (20–38%). In the products obtained from the reaction with α,β-unsaturated aldehydes, the de could be determined on the basis of the relative intensities of the aldehydic protons of the two diastereomers. Theoretical investigations of the reaction of (S)-(–)-α-methylbenzylamine with trans-cinnamaldehyde at the DFT (B3LYP/6-31+G*) level reveal that the diastereomer formed from the attack of the amine on the Re face is thermodynamically more stable. The calculations also show that the aldehydic proton of this diastereomer is expected to be more deshielded, which on the basis of the 1H NMR spectrum is the major product.

Supporting Information

 
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