Photochemical rearrangement of diene endoperoxides

Efficient synthesis of polysubstituted isochromanones via a novel photochemical rearrangement.

A novel and convenient approach to the synthesis of polysubstituted isochromanones is described. Irradiation of 2-formyl phenylalkeno-derivatives with UV light in benzene solution afforded the corresponding products in up to 98% yield. The possible reaction mechanism is proposed and further supported by the isotopic experiments.

Exploring endoperoxides as a new entry for the synthesis of branched azasugars

A new class of nitrogen-containing endoperoxides were synthesised by a photochemical [4 + 2]-cycloaddition between a diene and singlet oxygen. The endoperoxides were dihydroxylated and protected to provide a series of endoperoxide building blocks for organic synthesis, with potential use as precursors for the synthesis of branched azasugars. Preliminary exploration of the chemistry of these bui...

Rh-Catalyzed rearrangement of vinylcyclopropane to 1,3-diene units attached to N-heterocycles

Dienes embedded in quinolizidine and indolizidine structures can be prepared in four steps from cyclic nitrones and bicyclopropylidene. The key intermediates α-spirocyclopropanated N-heterocyclic ketones, generated via a domino 1,3-dipolar cycloaddition/thermal rearrangement sequence, were converted by Wittig methylenation to the corresponding vinylcyclopropanes (VCPs), which underwent rearrang...

Enantioselective synthesis of gamma-hydroxyenones by chiral base-catalyzed Kornblum DeLaMare rearrangement.

A cinchona-alkaloid catalyzed asymmetric Kornblum DeLaMare rearrangement has been developed. Thus, enantioenriched 4-hydroxyenones are prepared from dienes by a two-step sequence involving photochemical dioxygenation and chiral base-catalyzed desymmetrization of the resulting endoperoxides.

Photochemical preparation of pyrrole ring-contracted chlorins by the Wolff rearrangement.