Bifunctionalized Allenes, VII: Two Methods for One‐Pot Synthesis of Sulfonyl‐Functionalized Allenecarboxylates and Phosphorylated Allenes

Abstract

Two new approaches to the synthesis of sulfonyl‐functionalized allenecarboxylates and phosphorylated allenes are described. 2‐Sulfonyl‐alka‐2,3‐dienoates were readily prepared in an one‐pot reaction by [2,3]‐sigmatropic rearrangement of sulfinato‐substituted 2‐alkynoates, in situ generated from ethyl propynoate and subsequent treatment with lithium diisopropyl (LDA), ketone, trimethylchlorosilane (TMSCl), and the corresponding sulfinyl chlorides. Preparation of 1‐sulfonyl‐alka‐1,2‐dienephosphonates and ‐1,2‐dienyl phosphine oxides consists of the reaction of the lithio compounds, in situ generated from phosphorylated allenes and LDA, with the corresponding sulfonyl chlorides.

Keywords:

• [2,3]‐Sigmatropic rearrangement
• 1‐sulfonyl‐alka‐1,2‐dienephosphonates
• 1‐sulfonyl‐alka‐1,2‐dienyl phosphine oxides
• 2‐sulfonyl‐alka‐2,3‐dienoates
• synthesis

Acknowledgments

Financial support from the Research Fund of the University of Shumen (Project Nos. 33/2004 and 30/2005) is acknowledged.