Synthesis of 2,3-Dihydroxyhex-4-enoates by Palladium-Catalyzed Allylic Alkylations of Carbohydrate Derived Vinyl Lactones

Abstract

d-Gulonic lactone or its l-isomer is easily converted to the vinyl lactone 1 via three convenient reactions in an overall 69% yield. Reaction of the d isomer of 1 with a variety of carbon, oxygen, sulfur, and nitrogen nucleophiles and a palladium catalyst produced carboxylic acids that were esterified with methyl iodide to give the esters 2. Alternatively, reaction of l-lactone 1 with Ph₃P=CHCO₂Et provided the Wittig product that underwent palladium-catalyzed rearrangement to give the cyclopentanone 3.

Key words

gulonic lactone - rearrangement - π-allyl - allylic alkylation - palladium

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