Synthesis, structure and pyrolysis of stabilised phosphonium ylides containing saturated oxygen heterocycles

Robert Alan Aitken; Nazira Karodia; Hollie B McCarron; Cécile Rouxel; Nina Sahabo; Alexandra Martha Zoya Slawin

doi:10.1039/C5OB02467F

Synthesis, structure and pyrolysis of stabilised phosphonium ylides containing saturated oxygen heterocycles

Robert Alan Aitken, Nazira Karodia, Hollie B McCarron, Cécile Rouxel, Nina Sahabo, Alexandra Martha Zoya Slawin

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	English
Pages (from-to)	1794-1804
Number of pages	11
Journal	Organic & Biomolecular Chemistry
Volume	14
Issue number	5
DOIs	https://doi.org/10.1039/C5OB02467F
Publication status	Published - 7 Feb 2016

Access to Document

10.1039/C5OB02467F

Aitken_2015_OBC_Synthesis_CC
Copyright 2015 the Authors. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (http://creativecommons.org/licenses/by/3.0/).
Final published version, 624 KBLicence: CC BY

Cite this

@article{8d964b5019ee4319a50cfb692210f7bd,

title = "Synthesis, structure and pyrolysis of stabilised phosphonium ylides containing saturated oxygen heterocycles",

abstract = "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.",

author = "Aitken, {Robert Alan} and Nazira Karodia and McCarron, {Hollie B} and C{\'e}cile Rouxel and Nina Sahabo and Slawin, {Alexandra Martha Zoya}",

year = "2016",

month = feb,

day = "7",

doi = "10.1039/C5OB02467F",

language = "English",

volume = "14",

pages = "1794--1804",

journal = "Organic & Biomolecular Chemistry",

issn = "1477-0520",

publisher = "Royal Society of Chemistry",

number = "5",

}

TY - JOUR

T1 - Synthesis, structure and pyrolysis of stabilised phosphonium ylides containing saturated oxygen heterocycles

AU - Aitken, Robert Alan

AU - Karodia, Nazira

AU - McCarron, Hollie B

AU - Rouxel, Cécile

AU - Sahabo, Nina

AU - Slawin, Alexandra Martha Zoya

PY - 2016/2/7

Y1 - 2016/2/7

N2 - 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.

AB - 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.

UR - http://www.rsc.org/suppdata/c5/ob/c5ob02467f/c5ob02467f1.pdf

UR - http://www.rsc.org/suppdata/c5/ob/c5ob02467f/c5ob02467f2.cif

U2 - 10.1039/C5OB02467F

DO - 10.1039/C5OB02467F

M3 - Article

SN - 1477-0520

VL - 14

SP - 1794

EP - 1804

JO - Organic & Biomolecular Chemistry

JF - Organic & Biomolecular Chemistry

IS - 5

ER -

Synthesis, structure and pyrolysis of stabilised phosphonium ylides containing saturated oxygen heterocycles

Abstract

Access to Document

Other files and links

Fingerprint

Structuring the Future: Structuring the Future - Underpinning world-leading science in EaStCHEM through cutting edge characterisation

Upgrade Small Equipment Base: Small items of research equipment at the University of St Andrews. Supporting a new generation of physical sciences research