Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, USA.
J Org Chem. 2010 Mar 5;75(5):1693-700. doi: 10.1021/jo902685x.
Herein we describe density functional theory calculations on nitroso acetal-to-aminal rearrangements reported by Denmark and co-workers. Our calculations indicate that various structural (ring strain, hyperconjugation, anomeric effects) and environmental (both specific and nonspecific solvation) factors greatly influence the ease of rearrangement. Our calculations also indicate that both concerted and stepwise mechanisms are energetically viable.
在此，我们描述了由 Denmark 及其同事报道的亚硝酮缩醛到缩胺的重排的密度泛函理论计算。我们的计算表明，各种结构（环应变、超共轭、端基效应）和环境（包括特异性和非特异性溶剂化）因素极大地影响重排的容易程度。我们的计算还表明，协同和分步机制在能量上都是可行的。
