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.

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: Jul 8, 2014
• 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
• Public URL: https://durham-repository.worktribe.com/output/1448460