The
highly Lewis basic amidine-based catalyst DHIP promotes the
rearrangement of S-phenacyl thiocinnamate and related
thioesters into dihydrothiophene derivatives. In contrast to previously
explored rearrangements of thioesters, the reaction proceeds via a
novel Dieckmann-like cyclization pathway. An alternative two-component
synthesis of the same products has also been developed.
Several additional examples of cascade cyclizations of α,β-unsaturated thioesters proceeding are reported, which proceed via two distinct mechanistic pathways: enantioselective acyl transfer promoted by amidine-based catalysts (ABCs) and a racemic chain mechanism mediated by a thiolate nucleophile. Note pubs.acs.org/joc
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