2,6-Difluorophenylnitrene was reinvestigated both experimentally, in Ar matrices at 10 K, and computationally, by DFT and CASSCF/CASPT2 calculations. Almost-pure samples of both neutral rearrangement products (the bicyclic azirine and the cyclic ketenimine) of a phenylnitrene were prepared and characterized for the first time. These samples were then subjected to X-irradiation in the presence o...

ortho-Quinone methides, arising from a formal [2+2] cycloaddition between arynes and DMF, were found to facilely undergo a [4+2] cycloaddition with ester enolates or ketenimine anions to produce diverse coumarins in a straightforward manner.

Both flash vacuum thermolysis (FVT) and matrix photolysis generate 2-diazomethylpyrazine (22) from 1,2,3-triazolo[1,5-a]pyrazine (24). FVT of 4-azidopyridine (18) as well as of 24 or 2-(5-tetrazolyl)pyrazine (23) affords the products expected from the nitrene, i.e., 4,4'-azopyridine and 2- and 3-cyanopyrroles. Matrix photolyses of both 18 and 24 result in ring expansion of 4-pyridylnitrene/2-py...

The addition of acetonitrile, propionitrile, and acrylonitrile to tetramesityldigermene was investigated and compared to the addition of acetonitrile and acrylonitrile to germanium dimers on the Ge(100)-2×1 surface. In each case, a 1,2,3-azadigermetine was formed as the major product. As on the surface, the addition of nitriles to digermenes was found to be reversible, providing the first examp...

A three-component reaction involving diphosphinoketenimines, isocyanides and water or ethanol leading to the formation of new five-membered azaphosphaheterocycles is described.

A novel synthesis of α,β-unsaturated amides from N,N-disulfonyl ynamides with aldehydes was developed. By utilization of salicylaldehydes, a variety of substituted iminocoumarins were prepared.

A Diels-Alder reaction between cyclopentadiene and a variety of ketenimines is reported. A copper(I)-bis(phosphine complex catalyzes the cycloaddition across the C═N bond of the ketenimine in a [4 + 2] reaction to give an enamine intermediate that is hydrolyzed upon purification to generate aminoketones.

It is quite possible that ketenimine is formed, as predicted by the authors, in a concerted reaction in the thermolysis of vinyl azide with a barrier of ca. 38 kcal/mol. However, the theoretical treatment is inappropriate as regards the potential vinylnitrene intermediate or transition state, since singlereference methods such as DFT or MP2 cannot provide a correct description. It is now well-k...

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