No abstract

The reaction of PdCl2(PhCN)2 with ethyl α-N-acetyl-β-(4,6-dimethylbenzofuran-2-yl)acrylate, having a Z-propenyl group at 2-position of benzofuran ring, gave an azepine derivative, whereas its E-isomer afforded a Pd-σ-complex having azepine skeleton. Configurational assignment of the σ-complex, accomplished by methoxycarbonylation, clearly demonstrates that this intramolecular aminopalladation proceeds via cis-aminopalladation.

No abstract

Thermal reaction of 2H-azirines, bearing a methoxy or methylthio group at the neighboring position to azirine ring, was studied. In thermolysis of ethyl 2-(2-methoxynaphth-1-yl)-2H-azirine-3-carboxylate, attack of the vinyl nitrene at the peri position to form a 1-azaphenalene ring was observed. In thermal reaction of its thio analogue, 1-azaphenalene was also formed, but a naphthothiazine formed by the attack of vinyl nitrene at the sulfur atom was the major product. Mechanisms and differences of the reactions depending on O and S are discussed.

108ChemInform Abstract Thermolysis of the α-azidoacrylates (I) yields a mixture of the fused pyrroles (II) and the fused pyridines (III). When the related azides (IV) are thermolyzed, the anellated pyrroles (V) are the major or sole products. (Intermediates).