N-substituted akyl- and nonalkylpiperidines: Equatorial, axial or intermediate conformations?

被引：14

作者：

Tran Dinh Phien ^{[1
]}

Shlykov, Sergey A. ^{[1
]}

机构：

[1] Ivanovo State Univ Chem & Technol, Res Inst Thermodynam & Kinet Chem Proc, Dept Phys & Colloidal Chem, Sheremetev Ave 7, Ivanovo 153000, Russia

来源：

COMPUTATIONAL AND THEORETICAL CHEMISTRY | 2016年 / 1087卷

基金：

俄罗斯基础研究基金会;

关键词：

N-substituted piperidines; Conformational properties; Quantum chemical calculations; Nitrogen inversion; Ring inversion; Molecular structure; NONBONDING ELECTRON-PAIR; LOW-TEMPERATURE NMR; SATURATED HETEROCYCLES; MOLECULAR-STRUCTURE; 6-MEMBERED RINGS; NITROGEN INVERSION; AB-INITIO; PIPERIDINE; EQUILIBRIUM; SPECTROSCOPY;

D O I：

10.1016/j.comptc.2016.04.025

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Detailed quantum chemical calculations for a series alkyl- and nonalkyl-derivatives were performed continuing a systematic study of N-substituted piperidines. Three groups have been proposed to sort out the compounds distinguishing from each other by preference of the substituent's position: (a) adopting exclusively equatorial position (alkylpiperidines); (b) with no exceptional priority of any of the conformers; (c) a peculiar group for which the terms 'equatorial and axial' are not applicable the nitrogen bond configuration is planar or nearly planar (formyl, carbonyl, etc.). Geometry, pathways and barriers for nitrogen and ring inversions were calculated. Most of the MP2 calculations predict higher axial form contribution as compared with those by DFT-B3LYP. (C) 2016 Elsevier B.V. All rights reserved.

引用

页码：26 / 35

页数：10

共 51 条

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