Horner Olefination Reaction in Organic Sulfur Chemistry and Synthesis of Natural and Bioactive Products

Abstract

This article outlines the results of our work on the application of the Horner olefination reaction for the synthesis of unsaturated sulfur compounds. A general synthesis of racemic and optically-active α,β-unsaturated sulfoxides by the Horner reaction with α-sulfinylmethylphosphonates as olefination reagents is presented. We demonstrated how the structure of the phosphonate moiety may control the E- and Z-stereoselectivity in the above reaction. The use of racemic and optically-active α-sulfinylvinylphosphonates in tandem Michael addition/Horner olefination reaction leads to a wide range of carbocyclic and heterocyclic vinyl sulfoxides. In second part of this account a new strategy for the synthesis of functionalized cyclopentenones is briefly described. The synthesis and reactivity of 3-phosphorylmethyl-cyclopentenones is discussed as a platform for developing the synthesis of racemic rosaprostol, enantiomeric prostaglandin B₁ methyl esters, enantiopure isoterreins, natural and unnatural neplanocin A and enantiomeric forms of phytoprostane B ₁ type I.

Keywords:

• Horner reaction
• α-sulfinylalkylphosphonates
• vinyl sulfoxides
• 3-phosphorylmethyl-cyclopentenones
• total synthesis
• natural products
• phytoprostane B₁ type I

Acknowledgments

This paper is based on the keynote lecture presented at the 17th International Conference on Phosphorus Chemistry (Xiamen, China), and it is dedicated to the late Professor Leopold Horner.

Financial support from the Ministry of Science and Higher Education (Grant No PBZKBN-126/T09/2004 to M. M.) is gratefully acknowledged.