Synthesis, structure and pyrolysis of stabilised phosphonium ylides containing saturated oxygen heterocycles
MetadataShow full item record
A range of twelve stabilised phosphonium ylides containing tetrahydrofuran, tetrahydropyran or 2,2-dimethyl-1,3-dioxolane rings have been prepared and fully characterised, including one X-ray structure determination of each type. The X-ray structures confirm the P=C and C=O functions to be syn and all the compounds undergo thermal extrusion of Ph3PO to give the corresponding alkynes. In some cases there is also competing loss of Ph3P to give different carbene-derived products and evidence has been obtained for the generation of 2-phenyloxete in this way. Raising the pyrolysis temperature leads in several cases to new secondary reactions of the alkyne products involving a sequence of alkyne to vinylidene isomerisation, intramolecular CH insertion, and retro Diels Alder reaction.
Aitken , R A , Karodia , N , McCarron , H B , Rouxel , C , Sahabo , N & Slawin , A M Z 2016 , ' Synthesis, structure and pyrolysis of stabilised phosphonium ylides containing saturated oxygen heterocycles ' Organic & Biomolecular Chemistry , vol 14 , no. 5 , pp. 1794-1804 . DOI: 10.1039/C5OB02467F
Organic & Biomolecular Chemistry
Copyright 2015 the Authors. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (http://creativecommons.org/licenses/by/3.0/).
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.