Rhodium-Catalyzed Double Dearomatization of 1,2,3-Triazole-Isoxazole Dyads: Synthesis of Nonfused 1-1,3-Diazepines.

A double dearomatization of dyads consisting of 1-sulfonyl-1,2,3-triazoles and 3-aryl-5-methoxyisoxazoles was applied for the efficient synthesis of nonfused 1-1,3-diazepines. The plausible mechanism of the cascade reaction includes transformation of the 1,2,3-triazole to rhodium azavinyl carbene, the -selective hydride shift to form the 1-azabuta-1,3-diene moiety, rhodium-catalyzed ring contraction of the isoxazole to azirine, and pseudopericyclic four-atom ring expansion of the azirine. The synthetic utility and antiproliferative activity of the 1,3-diazepines obtained have been demonstrated.

Gold vs Light: Chemodivergent Reactivity of Diazoesters toward 2-Azirine-2-carboxylic Acids.

An orthogonal reactivity of diazo compounds toward azirine-2-carboxylic acids, switching with the reaction conditions, is demonstrated. A gold-catalyzed reaction is N-selective and produces 1,3-oxazin-6-ones, whereas a blue light activation leads to O-H insertion products, azirine-2-carboxylic esters. The observed chemodivergence is explained by the metal-bound and metal-free carbenes exhibiting different electronic properties in these reactions.

Characteristics of Epoxy Composites Containing Carbon Nanotubes/Graphene Mixtures.

The paper considers the development of fillers representing mixtures of carbon nanotubes and graphene materials (graphene oxide and graphene nanoplatelets) in different mass ratios to modify epoxy resin. The graphene type and content effect on the dispersed phase particle effective sizes-both in aqueous suspensions and the resin-was analyzed. Hybrid particles were characterized by Raman spectroscopy and electron microscopy.

Synthesis of Imidazo[1,2-]pyridines via Near UV Light-Induced Cyclization of Azirinylpyridinium Salts.

An efficient one-pot synthesis of imidazo[1,2-]pyridines from 2-bromoazirines and pyridines has been developed. The construction of the bicyclic framework of imidazo[1,2-]pyridines occurs in two steps through the formation of (2-azirin-2-yl)pyridinium bromides followed by dehydrobrominative UV light-induced cyclization. The method can also be applied for the synthesis of imidazo[2,1-]isoquinolines.

Light-induced one-pot synthesis of pyrimidine derivatives from vinyl azides.

A one-pot procedure for the synthesis of tetrasubstituted dihydropyrimidine and pyrimidine derivatives from α-azidocinnamates was developed. The synthesis is based on the finding that the outcome of LED photolysis of α-azidocinnamates depends on the light wavelength employed. Blue light (455 nm) leads to the formation of 2H-azirines only, but violet light (395 nm), UV-A light (365 nm), or sunlight result in the transformation of the in situ formed 2H-azirines to 1,3-diazabicyclo[3.