Ene-diene transmissive cycloaddition reactions with singlet oxygen: the vinylogous gem effect and its use for polyoxyfunctionalization of dienes.

The singlet oxygen reactivities and regioselectivities of the model compounds 1b-d were compared with those of the geminal (gem) selectivity model ethyl tiglate (1a). The kinetic cis effect is k(E)/k(Z) = 5.2 for the tiglate/angelate system 1a/1a' without a change in the high gem regioselectivity.

A new directing mode for singlet oxygen ene reactions: the vinylogous gem effect enables a 1O2 domino ene/[4 + 2] process.

The singlet oxygen reactions of 4-methyl-2,4-hexadienoates E,E- and E,Z-4 proceed in a highly mode selective and regioselective domino process. The initial product is the allylic hydroperoxide 5 directed by a vinylogous gem effect. The subsequent (1)O2 [4 + 2] cycloaddition delivers a 3:2 diastereoisomeric mixture of 1,2-dioxanes 8 in a one-pot process.

Photoinduced electron-transfer chemistry of the bielectrophoric N-phthaloyl derivatives of the amino acids tyrosine, histidine and tryptophan.

The photochemistry of phthalimide derivatives of the electron-rich amino acids tyrosine, histidine and tryptophan 8-10 was studied with respect to photoinduced electron-transfer (PET) induced decarboxylation and Norrish II bond cleavage. Whereas exclusive photodecarboxylation of the tyrosine substrate 8 was observed, the histidine compound 9 resulted in a mixture of histamine and preferential Norrish cleavage. The tryptophan derivative 10 is photochemically inert and shows preferential decarboxylation only when induced by intermolecular PET.