Synthesis and Conformation Analysis of cis-1,2-Disubstituted Cyclododecanes

被引：0

作者：

韩翔宇

王明安

李太公

梁晓梅

董燕红

陈馥衡

王道全

机构：

[1] Department of Applied Chemistry China Agricultural University

[2] Beijing 100094 China

[3] Department of Applied Chemistry China Agricultural University

来源：

Chinese Journal of Structural Chemistry | 2007年 / 06期

基金：

中国国家自然科学基金;

关键词：

reduction; 2-monosubstituted cyclododecanone; cis-1; 2-substituted cyclododeca- ne; corner position carbonyl participation; conformation analysis;

D O I：

10.14102/j.cnki.0254-5861.2007.06.001

中图分类号：

O623.11 [饱和脂烃（石蜡、烷属烃）];

学科分类号：

070303 ; 081704 ;

摘要：

cis-1,2-Disubstituted cyclododecanes 2 were synthesized by sodium borohydride reduction of 2-monosubstituted cyclododecanones and their structures were confirmed by 1H- NMR, 13C NMR and elemental analysis. The higher cis-selectivity of NaBH4 reduction of 2- monosubstituted cyclododecanones was rationalized by the mode of “corner position carbonyl participation”. Crystal data for 2c: Mr = 263.21, monoclinic, space group P21/c, a = 1.11140(7), b = 2.62590(17), c = 0.91360(6) nm, β = 106.1840(10)°, V = 2.5606(3) nm3, Dc = 1.366 g/cm3, Z = 8, F(000) = 1104, μ(MoKα) = 3.182 mm-1, S = 0.837, the final R = 0.0460 and wR = 0.1033. Crystal X-ray diffraction analysis for 2c showed that its ring skeleton adopts [3333] conformation, in which the OH group presents at the side-exo position and the other one at the corner carbon. The 1H NMR data of 2 showed that 1-corner-R-2-side-exo-OH [3333] and 1-corner-OH-2-side- exo-R [3333] conformations coexist in dynamic equilibrium in the solution, but only the former presents in the crystal.

引用

页码：625 / 631

页数：7