Horner olefination reaction in organic sulfur chemistry and synthesis of natural and bioactive products

摘要

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 alpha,beta-unsaturated sulfoxides by the Horner reaction with alpha-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 alpha-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-phospholylmethyl-cyclopentenones is discussed as a platform for developing the synthesis of racemic rosaprostol, enantiomeric prostaglandin B-1 methyl esters, enantiopure isoterreins, natural and unnatural neplanocin A and enantiomeric forms of phytoprostane B-1 type I.