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- Title
Harnessing the Peterson Reaction for the Stereospecific Synthesis of Z‐Vinyl Ethers.
- Authors
Tromans, Jay; Zhang, Bian; Golding, Bernard T.
- Abstract
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 Z 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 (Z/E ratio: 99 : 1). (R,R)/(S,S)‐1‐alkoxy‐2‐hydroxyalkylsilanes were synthesized from 1‐trimethylsilylalkynes by a sequence of reduction with di‐isobutylaluminium hydride to a (Z)‐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 (R,R)/(S,S)‐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 Z 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 E isomer. The sequence described embraces a variety of substituents and precursors, proceeds in overall high yield and is readily scalable.
- Subjects
STEREOSPECIFICITY; ETHER synthesis; AFLATOXINS; POLAR solvents; RING-opening reactions; VINYL ethers; ISOMERS
- Publication
Chemistry - A European Journal, 2024, Vol 30, Issue 2, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202302708