70156-86-4Relevant articles and documents
Photocatalyzed Generation of Nitrosocarbonyl Intermediates Under Solar Light Irradiation
Basile, Teresa,Capaldo, Luca,Ravelli, Davide,Quadrelli, Paolo
, p. 1443 - 1447 (2019/06/08)
Tetrabutylammonium decatungstate (TBADT) has emerged as a valuable photocatalyst for sunlight-induced organic reactions. In this communication we wish to present its use for the photocatalytic oxidation of hydroxamic acids to generate fleeting nitrosocarb
Hetero Diels–Alder Reaction and Ene Reaction of Acylnitroso Species in situ Generated by Hypoiodite Catalysis
Uraoka, Saki,Shinohara, Ikumi,Shimizu, Hisato,Noguchi, Keiichi,Yoshimura, Akira,Zhdankin, Viktor V.,Saito, Akio
supporting information, p. 6199 - 6203 (2018/11/10)
As a first non-metal-catalyzed oxidation for the in situ generation of acylnitroso species, we describe the hypoiodite catalysis using tetra-n-butylammonium iodide as precatalyst with tert-butyl hydroperoxide or hydrogen peroxide as a terminal oxidant. Th
An Experimental and Computational Approach to Understanding the Reactions of Acyl Nitroso Compounds in [4 + 2] Cycloadditions
Chaiyaveij, Duangduan,Batsanov, Andrei S.,Fox, Mark A.,Marder, Todd B.,Whiting, Andrew
, p. 9518 - 9534 (2015/10/12)
Catalytic aerobic oxidation of phenyl hydroxycarbamate 1 and 1-hydroxy-3-phenylurea 2 using CuCl2 and 2-ethyl-2-oxazoline in methanol gave acyl nitroso species in situ, which were trapped in nitroso-Diels-Alder (NDA) reactions with various dienes to afford the corresponding cycloadducts in high yields (90-98%). Competing ene products were also present for dienes containing both alkene π-bonds and allylic σ-bonds, and the ene yields are higher with 1 than with 2. The use of the chiral hydroxamic acid, (R)-1-hydroxy-3-(1-phenylethylurea) 3 (same conditions) gave NDA cycloadducts in high yields (97-99%) with no ene product from 2,3-dimethyl-1,3-butadiene. NDA cycloadducts were not obtained from other hydroxamic acid analogues [RCONHOH (R = PhCH2 4; Ph(CH2)2 5; Ph(CH2)3 6; Ph(CH2)4 7; Ph 8; 2-pyridyl 9; 3-pyridyl 10] with various dienes using copper-oxidation but rather were obtained using sodium periodate, resulting in variable NDA yields (13-51%) from hydroxamic acids 1-10 with cyclohexa-1,3-diene and 2,3-dimethyl-1,3-butadiene (several cycloadducts characterized by X-ray crystallography). The NDA and nitroso-ene reaction pathways of nitroso intermediates with dienes were mapped by DFT computations (B3LYP/6-31G), which showed that the acyl nitroso species are super-reactive and that activation energies in the NDA processes are lower than the isomerization barriers between some cis- and trans-butadienes.