A New Method of Formation of Tributyl‐β‐ keto‐ and Tributyl‐β‐alkoxycarbonylalkylidenephosphorane from Tributyl[(trimethylsilyl) methylene]phosphorane and Their Application in the Wittig Reaction. Issue 3 (12th November 2014)

• Record Type: Journal Article
• Authors: Łukaszewicz, Ewa; Skrzyńska, Anna; Majewski, Piotr
• Is Part Of: Heteroatom chemistry. Volume 26:Issue 3(2015)
• Page Start: 194
• Page End: 198
• Publication Date: 2014-11-12
• Subjects: Heterocyclic chemistry -- Periodicals; 547.59
• DOI: 10.1002/hc.21246
• Languages: English
• ISSNs: 1042-7163

Abstract

<abstract abstract-type="main"> <title>ABSTRACT</title> <p>A new and efficient method of the synthesis of tributyl‐β‐keto‐ and tributyl‐β‐alkoxycarbonylalkylidenephosphorane via treatment of tributyl[(trimethylsilyl)‐ methylene]phosphorane with acid chlorides or chloroformate is described. These compounds have been studied less often than their triphenyl analogues (Maryanoff and Reitz, <italic>Chem Rev</italic> 1989, 89, 870; Taillefer and Cristau, <italic>Top Curr Chem</italic>, 2003, 229, 41; Appel, Loos, and Mayr, <italic>J Am Chem Soc</italic> 2009, 131, 704) because trialkyl‐stabilized ylides are very reactive, highly perishable, and more difficult to synthesize. This paper also presents the reaction of in situ generated tributyl‐β‐keto‐ and tributyl‐β‐alkoxycarbonylalkylidenephosphoranes with <italic>p</italic>‐nitrobenzaldehyde as a model aldehyde to obtain α, β‐unsaturated ketones and esters. All reactions result in Wittig products in a completely <italic>E</italic>‐stereoselective manner.</p> </abstract>