From Ring-Expansion to Ring-Contraction: Synthesis of γ-Lactones from Cyclobutanols and Relative Stability of Five- and Six-Membered Endoperoxides toward Organic Bases

Abstract

Cyclobutanols undergo ring expansion with molecular oxygen in the presence of Co(acac)₂ to afford 1,2-dioxane-hemiperoxyketals. In the course of acylation, we observed that endoperoxides rearranged into γ-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.

Key words

peroxides - ring contraction - ring-expansion - lactones - fragmentations - rearrangement - heterocycles

Publication History

Received: 03 December 2021

Accepted after revision: 07 February 2022

Accepted Manuscript online:
07 February 2022

Article published online:
24 March 2022

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