通过 Prins-pinacol 反应构建 12-氧杂三环[6.3.1.0(2,7)]十二烷环体系中的立体控制起源。
Origin of stereocontrol in the construction of the 12-oxatricyclo[6.3.1.0(2,7)]dodecane ring system by Prins-pinacol reactions.
机构信息
Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, California 92697-2025, USA.
出版信息
J Org Chem. 2010 Jan 15;75(2):455-63. doi: 10.1021/jo9024144.
Abstract
Polycyclic products containing the 12-oxatricyclo[6.3.1.0(2,7)]dodecane moiety having either the trans (8a-e) or cis (9a-e) relative configuration of the oxacyclic bridge and the cis angular substituents are formed stereospecifically by Prins-pinacol cyclizations of unsaturated alpha-dithianyl acetals 14a-e or 15a-e. These results show that the topography (boat or chair) of the Prins cyclization of the sulfur-stabilized oxocarbenium ions generated from acetals 14a-e or 15a-e is controlled by the stereoelectronic influence of the allylic substituents, with steric effects playing a minor role. A complex molecular rearrangement that is terminated by a thio-Prins-pinacol reaction is also identified.
摘要
多环产物含有 12-氧杂三环[6.3.1.0(2,7)]十二烷部分，其氧杂环桥的反式（8a-e）或顺式（9a-e）相对构型和顺式角取代基通过不饱和α-二噻烷基缩醛 14a-e 或 15a-e 的 Prins-频哪醇环化反应立体特异性形成。这些结果表明，从缩醛 14a-e 或 15a-e 生成的硫稳定氧碳翁离子的 Prins 环化的地形学（船或椅）受烯丙基取代基的立体电子影响控制，空间效应的作用较小。还鉴定了一种通过硫-Prins-频哪醇反应终止的复杂分子重排。
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