Abstract

A skeletal rearrangement of a series of 6,8-dioxabicyclo[3.2.1]octan-4-ols has been developed using SOCl₂ in the presence of pyridine. An oxygen migration from C5 to C4 was observed when the C4 alcohols were treated with SOCl₂/pyridine, giving a 2-chloro-3,8-dioxabicyclo[3.2.1]octane ring-system via the chlorosulfite intermediate. Analogous allylic alcohols with endocyclic and exocyclic unsaturations underwent chlorination without rearrangement due to formation of allylic cations. The rearrangement was also demonstrated using Appel conditions, which gave similar results via the alkoxytriphenylphosphonium intermediate. Several reactions of the products were investigated to show the utility of the rearrangement.

Beilstein J. Org. Chem. 2024, 20, 823–829. doi:10.3762/bjoc.20.74

摘要

在吡啶存在下使用 SOCl ₂开发了一系列 6,8-二氧杂双环[3.2.1]辛烷-4​​-醇的骨架重排。当C4醇用SOCl ₂ /吡啶处理时，观察到氧从C5迁移到C4 ，通过氯亚硫酸盐中间体得到2-氯-3,8-二氧杂双环[3.2.1]辛烷环系统。具有环内和环外不饱和度的类似烯丙醇进行氯化，而不会由于形成烯丙基阳离子而发生重排。还使用 Appel 条件证明了重排，通过烷氧基三苯基鏻中间体得到了类似的结果。研究了产物的几种反应以显示重排的效用。

贝尔斯坦 J. 组织。化学。 2024, 20, 823–829。 doi:10.3762/bjoc.20.74