Polycyclic ethers and an unexpected dearomatisation reaction during studies towards the bioactive alkaloid, perophoramidine

TETRAHEDRON

卷:74

Article; Proceedings Paper

Westwood, Nicholas J.¹ 

[1] Univ St Andrews, Sch Chem, St Andrews KY16 9ST, Fife, Scotland

关键词: Natural product;    Ring opening reaction;    Cyclic ether;    Dearomatisation;   

DOI  :  10.1016/j.tet.2018.04.086

来源: Elsevier

【 摘 要 】

The bioactive alkaloid natural product perophoramidine and the related family of compounds known as the communesins have inspired the synthesis community for more than a decade. Many of the elegant approaches have required the synthesis of complex intermediates that have not always reacted in the expected manner. In this study we describe a series of cyclic ether-containing precursors that were prepared during our synthetic studies towards these natural products. Attempts to open the cyclic ether ring and trap the resulting stabilised carbocation with a carbon nucleophile ultimately led to the preparation of a diallyl-substituted all carbon quaternary centre. Subsequent attempts to differentiate between the two allyl groups resulted in a relatively clean transformation to an unexpected compound. Extensive structural characterisation, including small molecule X-ray crystallography, showed that a dearomatisation reaction had occurred. (C) 2018 Elsevier Ltd. All rights reserved.

【 授权许可】

Free