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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 VincenteTosylhydrazones 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.
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Publication status
- Published
Journal
Journal of the American Chemical SocietyISSN
0002-7863Publisher
ACS PublicationsExternal DOI
Issue
20Volume
125Page range
6034-6035Pages
2.0Department 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
2012-02-06Usage metrics
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