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.
Professor Andrew Whiting email@example.com
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.
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||Jul 8, 2014|
|Journal||Journal of Organic Chemistry|
|Publisher||American Chemical Society|
|Peer Reviewed||Peer Reviewed|
Accepted Journal Article
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