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Generation of phosphoranes derived from phosphites. A new class of phosphorus ylides leading to high E selectivity with semi-stabilizing groups in Wittig olefinations

journal contribution
posted on 2023-06-08, 09:34 authored by Varinder K Aggarwal, J Robin Fulton, Chris G Sheldon, Javier de Vincente
Tosylhydrazones derived from aryl aldehydes react with t-BuOK, ClFeTPP, (MeO)3P, and aldehydes to furnish olefins with high E selectivity. These reactions occur through a Wittig-type pathway via the corresponding diazo compounds, metal carbenes and phosphorous ylides, with the water-soluble trimethyl phosphate as the byproduct. Similar reactions can also be performed using ethyl diazoacetate; however, high E selectivity was only observed in the presence of LiBr. In this case, the reaction is believed to occur via the phosphonate anion, formed through an Arbuzov reaction. Thus this olefination reaction occurs through a Horner-Wadsworth-Emmons (HWE) reaction but the phosphonate anion is generated under completely base-free conditions.

History

Publication status

  • Published

Journal

Journal of the American Chemical Society

ISSN

0002-7863

Publisher

ACS Publications

Issue

20

Volume

125

Page range

6034-6035

Pages

2.0

Department affiliated with

  • Chemistry Publications

Notes

First example using phosphite ylides in Wittig olefination reactions. Unexpectedly high E selectivity was observed, JRF carried out additional studies to understand these results. JRF contributed both to the results and writing of the manuscript in collaboration C. G. Sheldon. Cited over 40 times.

Full text available

  • No

Peer reviewed?

  • Yes

Legacy Posted Date

2012-02-06

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