期刊
SYNTHESIS-STUTTGART
卷 54, 期 12, 页码 2816-2824出版社
GEORG THIEME VERLAG KG
DOI: 10.1055/a-1765-1615
关键词
peroxides; ring contraction; ring-expansion; lactones; fragmentations; rearrangement; heterocycles
资金
- Ministere de l'Enseignement Superieur, de la Recherche et de l'Innovation (MESRI)
This study reports the ring expansion reaction of cyclobutanols with molecular oxygen and the generalization of ring contraction through a rearrangement reaction. It also reveals the difference in stability between 1,2-dioxane and 1,2-dioxolane against organic bases.
Cyclobutanols undergo ring expansion with molecular oxygen in the presence of Co(acac)(2) to afford 1,2-dioxarie-hemiperoxyketals. In the course of acylation, we observed that endoperoxides rear-ranged into gamma-lactone in the presence of triethylamine. Thus, a generalization of this ring contraction through a Kornblum-DeLaMare rearrangement is here reported. Application of this transformation to monosubstituted 1,2-dioxane derivatives also led to 1,4-ketoaldehydes, in proportions depending on the nature of the substituent. These same conditions applied to five-membered dioxolane analogues led to fragmentation instead, through a retro-aldol type process. This study emphasizes the difference of stability of 1,2-dioxane and 1,2-dioxolane against organic bases, 1,2-dioxolanes having proved to be particularly reactive whereas 1,2-dioxanes showed a relative tolerance under these conditions.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据