Kolocouris A, Outeiriño J G, Anderson J E, Fytas G, Foscolos G B, Kolocouris N
Department of Pharmaceutical Chemistry, School of Pharmacy, University of Athens, Panepistimioupoli-Zografou, GR 15 771 Athens, Greece.
J Org Chem. 2001 Jul 27;66(15):4989-97. doi: 10.1021/jo0016677.
When a 1-adamantyl or a 2-adamantyl substituent is introduced at the 2-position in N-methylpiperidine, four different chair conformations are possible. Experimental observation using dynamic NMR spectroscopy and molecular mechanics calculations agree that the chair conformation with an equatorial adamantyl group and an axial methyl group is by far the most stable, but in both cases a minor population of a second conformation is demonstrated and characterized. Interaction between adamantyl and methyl groups is much more conformation-determining than any preference for equatorial over axial location which predominates in simpler 2-substituted N-methylpiperidines.
当在N-甲基哌啶的2-位引入1-金刚烷基或2-金刚烷基取代基时，可能存在四种不同的椅式构象。使用动态核磁共振光谱的实验观察和分子力学计算均表明，具有平伏金刚烷基和直立甲基的椅式构象是迄今为止最稳定的，但在这两种情况下，均证实并表征了少量的第二种构象。与简单的2-取代N-甲基哌啶中占主导的平伏位置优于直立位置的任何偏好相比，金刚烷基和甲基之间的相互作用对构象的决定性作用要大得多。
