Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Vinyl ethers are valuable synthetic intermediates which are also found as natural products, including aflatoxins, rifamycins and plasmalogens. The latter are ubiquitous phospholipids in human cells and contain a vinyl ether moiety with specifically <jats:italic>Z</jats:italic> configuration. Although numerous methods are available for synthesis of vinyl ethers, there is a lack of methods for obtaining Z isomers of molecules of the type RCH=CHOR’ that are applicable to plasmalogens. A variant of the Peterson reaction is described that generates such molecules with very high stereoselectivity (<jats:italic>Z</jats:italic>/<jats:italic>E</jats:italic> ratio: 99 : 1). (<jats:italic>R,R</jats:italic>)/(<jats:italic>S,S</jats:italic>)‐1‐alkoxy‐2‐hydroxyalkylsilanes were synthesized from 1‐trimethylsilylalkynes by a sequence of reduction with di‐isobutylaluminium hydride to a (<jats:italic>Z</jats:italic>)‐1‐trimethylsilylalkene, epoxidation of the alkene to a 2‐trimethylsilyl‐3‐substituted epoxide and regioselective, boron‐trifluoride catalyzed ring‐opening of the epoxide by reaction with an alcohol. Conversion of the (<jats:italic>R,R</jats:italic>)/(<jats:italic>S,S</jats:italic>)‐1‐alkoxy‐2‐hydroxyalkylsilanes to vinyl ethers (RCH=CHOR’) was achieved under basic conditions as in a standard Peterson reaction. However, near exclusive formation of a <jats:italic>Z</jats:italic> vinyl ether was only achieved when the reaction was performed using potassium hydride in the non‐polar solvent α,α,α‐trifluorotoluene, more polar solvents giving increasing amounts of the <jats:italic>E</jats:italic> isomer. The sequence described embraces a variety of substituents and precursors, proceeds in overall high yield and is readily scalable.</jats:p>