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Understanding α,β-unsaturated imine formation from amine additions to α,β-unsaturated aldehydes and ketones: an analytical and theoretical investigation

Calow, A.D.J.; Carbó, J.J.; Cid, J.; Fernández, E.; Whiting, A.

Understanding α,β-unsaturated imine formation from amine additions to α,β-unsaturated aldehydes and ketones: an analytical and theoretical investigation Thumbnail


Authors

A.D.J. Calow

J.J. Carbó

J. Cid

E. Fernández



Abstract

A combination of in situ IR spectroscopy (ReactIR) and DFT calculations have been used to understand what factors govern the selectivity in the addition of primary amines to α,β-unsaturated aldehydes and ketones, i.e., 1,2- versus 1,4-addition. It has been found that the 1,2-addition products (α,β-unsaturated imines following addition and elimination) usually predominate for most systems. However, exceptions, such as methyl vinyl ketone, selectively give 1,4-addition products. This has been rationalized by DFT calculations that show that major conformational effects are involved, controlled mainly by steric effects of carbonyl substituents, resulting in a model that provides simple and predictable preparation of α,β-unsaturated imines for in situ utilization in synthesis.

Citation

Calow, A., Carbó, J., Cid, J., Fernández, E., & Whiting, A. (2014). Understanding α,β-unsaturated imine formation from amine additions to α,β-unsaturated aldehydes and ketones: an analytical and theoretical investigation. Journal of Organic Chemistry, 79(11), 5163-5172. https://doi.org/10.1021/jo5007366

Journal Article Type Article
Acceptance Date Mar 31, 2014
Online Publication Date May 14, 2014
Publication Date Jun 1, 2014
Deposit Date Jul 3, 2014
Publicly Available Date Mar 29, 2024
Journal Journal of Organic Chemistry
Print ISSN 0022-3263
Electronic ISSN 1520-6904
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 79
Issue 11
Pages 5163-5172
DOI https://doi.org/10.1021/jo5007366

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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in the Journal of organic chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jo5007366





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