29809-24-3Relevant articles and documents
Evidence of a Nitrene Tunneling Reaction: Spontaneous Rearrangement of 2-Formyl Phenylnitrene to an Imino Ketene in Low-Temperature Matrixes
Nunes, Cláudio M.,Knezz, Stephanie N.,Reva, Igor,Fausto, Rui,McMahon, Robert J.
supporting information, p. 15287 - 15290 (2016/12/09)
Triplet 2-formyl phenylnitrene was generated by photolysis of 2-formyl phenylazide isolated in Ar, Kr, and Xe matrixes and characterized by IR, UV-vis, and EPR spectroscopies. Upon generation at 10 K, the triplet nitrene spontaneously rearranges in the dark to singlet 6-imino-2,4-cyclohexadien-1-ketene on the time scale of several hours. The intramolecular [1,4] H atom shift from the nitrene to the imino ketene occurs by tunneling, on the triplet manifold, followed by intersystem crossing. This case constitutes the first direct evidence of a tunneling reaction involving a nitrene.
Reduction of activated carbonyl groups using alkylphosphanes as reducing agents: A mechanistic study
Wei, Yin,Liu, Xu-Guang,Shi, Min
scheme or table, p. 2386 - 2393 (2012/06/04)
A comprehensive mechanistic investigation on the reduction of activated carbonyl groups using alkylphosphanes as reducing agents has been conducted through a combination of experimental as well as computational studies. Both approaches show that this kind of reduction proceeds either through proton transfer from alkylphosphanes and cleavage by water during work-up or through another reaction pathway involving the participation of water at the initial stage and a two-fold proton transfer to afford the product. The reaction mechanism of the reduction of activated carbonyl groups using alkylphosphanes has been studied both experimentally and theoretically. The reduction was shown to proceed either through proton transfer from alkylphosphanes and cleavage by water during work-up or through the participation of water at the initial stage and a two-fold proton transfer.
