Unlocking nature's antioxidants: a novel method for synthesising plasmalogens.

Plasmalogens are glycerophospholipids distinguished by their -()-vinyl ether at the -1 position. These lipids are implicated in several disease states requiring analytical, diagnostic and therapeutic interventions, which demand synthetic availability for a variety of structural types. By deploying the new -protecting group 1,4-dimethoxynaphthyl-2-methyl ('DIMON') and a new stereospecific method for accessing -vinyl ethers, a reproducible, versatile synthetic route to plasmalogens [plasmenyl phosphocholines] has been developed.

1,4-Dimethoxynaphthalene-2-methyl ('DIMON'), an oxidatively labile protecting group for synthesis of polyunsaturated lipids.

A new benzyl-type protecting group (1,4-dimethoxynaphthalene-2-methyl, 'DIMON') for hydroxyl functions can be selectively removed under oxidative conditions without damaging polyunsaturated fatty acyl groups. Its application is shown by the first synthesis of an ether (plasmanyl) phospholipid containing the docosa-(4,7,10,13,16,19)-hexaenoyl group.

Harnessing the Peterson Reaction for the Stereospecific Synthesis of Z-Vinyl Ethers.

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.