16042-85-6Relevant academic research and scientific papers
Regioselective CH bond activation on stabilized nitrogen ylides promoted by Pd(II) complexes: Scope and limitations
Grande, Loreto,Serrano, Elena,Cuesta, Luciano,Urriolabeitia, Esteban P.
scheme or table, p. 394 - 404 (2012/04/23)
The orthopalladation of N-ylides [HxCyN-CHC-(O)Ar] (HxCyN = pyridine, benzylamine, imidazole, aniline, and phenylpyridine; Ar = aryl) has been studied. The incorporation of the Pd atom to these substrates is regioselective, since the orthopalladation is produced, in most of the cases, only at the aryl ring of the benzoyl group with concomitant C-bonding of the Nylide. The X-ray structure of one representative example is reported. Factors governing the observed orientation are discussed, because this regioselectivity is worthy of note, considering the deactivating nature of the carbonyl group. Two exceptions to the general trend have been observed. The first one is the double metalation of the ylide [PhMe2NCHC(O)Ph], which incorporates one Pd at each Ph. The second one is the palladation of the phenylpyridine derivative, which occurs at the pyridinic 2-phenyl ring and produces a six-membered palladacycle.
Base-catalysed Rearrangements involvung Ylide Intermediates. Part 8. The Preparation and Some Reactions of Stable Ammonium Ylides
Jemison, Robert W.,Mageswaran, Sivapathasuntharam,Ollis, W. David,Sutherland, Ian O.,Thebtaranonth, Yodhathai
, p. 1154 - 1164 (2007/10/02)
The carbonyl-stabilised ammonium ylides (3), (12a-n), and (14a-c) were obtained from the reaction of the corresponding ammonium halides (1), (13a-n), and (15a-c) with sodium hydroxide in water or aqueous methanol.The ylides, which were characterised by their molecular formulae and spectroscopic properies, regenerated quaternary ammonium bromides on treatment with hydrobromic acid.In general the reactions of the ammonium ylides resemble those of the corresponding sulphonium ylides.Thus ylides having a suitable migrating group (ArCH2) undergo a Stevens rearrangement on heating, and other ylides fragment to give a tertiary amine and products containing the PhCOCH grouping.A number of ylides reacted with dimethyl acetylenedicarboxylate to give the furans (32).The ylides (14b and c) with phenyl isocyanate gave the phenylcarbamoyl-substituted ylides.
