Peter Metz

Reductive desulfurization of sultones prepared via intramolecular diels-alder reaction of a furan-containing vinylsulfonate

Abstract Treatment of sultone 1 and the saturated derivative 3 with strong bases or reaction of 1 with Red-Al caused a cleavage of the oxygen bridge. The resultant vinylic or allylic sultones 4 and 5 were efficiently desulfurized by metal/ammonia reduction. While a mixture of cyclohexenes 6 and 7 was produced from allylic sultones 5 , the vinylic sultones 4 reacted with complete regioselectivity to yield only 7 .

A synthetic approach to polyene macrolides. Macrolide and polyene generation

Abstract The 26-membered ring skeleton of tetrin-A has been synthesized using palladium based macrolactonization and elimination reactions.

Desulfurization of sultones with simultaneous methylenation

Abstract Desulfurization of the δ-sultones 2 with simultaneous formation of an exocyclic olefin is achieved by alkylation of 2 with (iodomethyl)trimethylsilane and subsequent treatment of the resultant products 7 with tetra-n-butylammonium fluoride. Application of this two-step procedure to sultone 8 leads to 1,3-diene 10, an intermediate for the synthesis of the highly oxygenated 1,10-seco-eudesmanolides eriolanin and eriolangin.

A synthetic approach to polyene macrolldes: Synthesis of the building blocks

Abstract The two building blocks required to construct the 26-membered ring skeleton of tetrin-A have been synthesized.

An intermediate for the total synthesis of guaianolides

Abstract A synthesis of an intermediate (5) for the construction of quaianolidesis described. The relative stereochemistry at C-1 and C-7 is established with complete stereocontrol.

Recent Advances in the Synthesis of Pamamycin-607

Using sultones as crucial intermediates, a short and highly stereoselective synthesis of a precursor of the larger fragment and the methyl ester of the smaller fragment of the macrodiolide pamamycin-607 was achieved.

Intramolecular Diels-Alder Reactions of Vinylsulfonates

Abstract Control of side chain chirality is efficiently achieved by intramolecular Diels-Alder cycloaddition of vinylsulfonates and subsequent oxidative or reductive desulfurization of the resultant sultones. An alkoxide directed regio- and stereoselective 1,6-addition to dienyl sultones further enhances the utility of this reaction sequence.

RECENT ADVANCES IN THE SYNTHETIC ELABORATION OF SULTONES

New methods for the elaboration of sultones enable a short and highly stereoselective synthesis of methyl nonactate and establish vinylsulfonyl chloride as an allene equivalent for the intramolecular Diels-Alder reaction.

an intermediate for the total synthesis of guaianolides; A correlation

Abstract The X-ray analyses of epoxy alcohol 2 and the immediate precursor of lactone 1 demand a revision of published hydroazulenic structures regarding their relative configuration at C-1.