Unequivocal experimental evidence for a unified lithium salt-free Wittig reaction mechanism for all phosphonium Ylide types: reactions with β-heteroatom-substituted aldehydes are consistently selective for cis-oxaphosphetane-derived products

Journal of the American Chemical Society
Peter A Byrne, Declan G Gilheany

Abstract

The true course of the lithium salt-free Wittig reaction has long been a contentious issue in organic chemistry. Herein we report an experimental effect that is common to the Wittig reactions of all of the three major phosphonium ylide classes (non-stabilized, semi-stabilized, and stabilized): there is consistently increased selectivity for cis-oxaphosphetane and its derived products (Z-alkene and erythro-β-hydroxyphosphonium salt) in reactions involving aldehydes bearing heteroatom substituents in the β-position. The effect operates with both benzaldehydes and aliphatic aldehydes and is shown not to operate in the absence of the heteroatom substituent on the aldehyde. The discovery of an effect that is common to reactions of all ylide types strongly argues for the operation of a common mechanism in all Li salt-free Wittig reactions. In addition, the results are shown to be most easily explained by the [2+2] cycloaddition mechanism proposed by Vedejs and co-workers as supplemented by Aggarwal, Harvey, and co-workers, thus providing strong confirmatory evidence in support of that mechanism. Notably, a cooperative effect of ortho-substituents in the case of semi-stabilized ylides is confirmed and is accommodated by the cycloaddit...Continue Reading

References

Dec 2, 2004·Journal of the American Chemical Society·Stephan A ReiterHubert Schmidbaur
Sep 30, 2005·Journal of the American Chemical Society·Raphaël RobietteJeremy N Harvey
Mar 1, 2006·Angewandte Chemie·David C HarrowvenLana Nanson
Nov 7, 2008·Angewandte Chemie·Norito TakenakaBurjor Captain
Aug 19, 2009·Angewandte Chemie·Christopher J O'BrienGregory A Chass

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Citations

Sep 28, 2013·Phytochemistry·Keisuke NishikawaMitsuru Shindo
Nov 26, 2013·Chemical Reviews·Rosana ÁlvarezÁngel R de Lera
Mar 17, 2016·Organic Letters·Martina SpallarossaJieping Zhu
Jul 9, 2016·The Journal of Organic Chemistry·Jaan SaameIvo Leito
Aug 11, 2016·The Journal of Organic Chemistry·Tomoya MatsushimaSoichiro Watanabe
Aug 9, 2016·Journal of the American Chemical Society·Peter A ByrneHerbert Mayr
Oct 21, 2016·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Anastasy O Kolodiazhna, Oleg I Kolodiazhnyi
Jan 20, 2016·Organic & Biomolecular Chemistry·Slavko RastBarbara Mohar
Dec 4, 2014·Chemical Communications : Chem Comm·Peter A ByrneDeclan G Gilheany
Sep 25, 2014·Angewandte Chemie·Emma E CoyleChristopher J O'Brien
Sep 29, 2012·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Satoaki OnitsukaJunji Inanaga
May 16, 2013·Chemical Society Reviews·Peter A Byrne, Declan G Gilheany
Jul 15, 2020·Chemistry : a European Journal·Ryoto InabaKensuke Naka
Mar 26, 2013·Chemistry : a European Journal·Christopher J O'BrienBryan J Doonan
Oct 12, 2013·Chemistry : a European Journal·Christopher J O'BrienKatherine C Przeworski
Jul 25, 2020·Organic & Biomolecular Chemistry·Nicolas D'ImperioSascha Ott
Sep 12, 2014·Journal of the American Chemical Society·Zhuo ChenDaniel A Singleton
May 15, 2015·The Journal of Organic Chemistry·Damian MyśliwiecMarcin Stępień
Oct 19, 2019·The Journal of Organic Chemistry·Paola FarfánAlbeiro Restrepo
Aug 30, 2013·The Journal of Organic Chemistry·Marcin Stępień
Dec 17, 2016·The Journal of Organic Chemistry·Zuyong DengJi-Chang Xiao
Nov 22, 2012·Journal of the American Chemical Society·Jesús García LópezFernando López Ortiz
Mar 27, 2013·Organic Letters·Sivappa RasapalliArnold L Rheingold
Jul 24, 2018·Journal of the American Chemical Society·Guillaume PovieKenichiro Itami

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