[3,3]Sigmatropic ring expansion of cyclic thionocarbonates. IV. Relationship between ring size of cyclic thionocarbonates and geometry of created double bond in medium- and large-membered thiolcarbonate

Article abstract of DOI:10.1248/cpb.39.1659

Medium- and large-membered cyclic thiolcarbonates containing an (E)- or (Z)-double bond were synthesized by two methods using [3,3]sigmatropic ring expansion of cyclic thionocarbonates. The [3,3]sigmatropic ring expansion proceeds exclusively via the transition state bearing the chain tethered in a cis relationship when the cyclic thionocarbonates are 8-membered or smaller. Importantly, the ring of the cyclic thionocarbonates determines the double bond geometry of the thiolcarbonate. Conversion of the cyclic thiolcarbonates into (E)- or (Z)-allylic sulfides is also described.

Full text of DOI:10.1248/cpb.39.1659

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