0000000000132206
AUTHOR
José Sepúlveda Arques
New cycloaddition reactions of 1-phenyl-4-vinylpyrazole
Abstract 1-Phenyl-4-vinylpyrazole reacts with methyl propiolate and N-phenylmaleimide giving via the Diels-Alder 1:1 adducts, products (4) and (8), and also the 1:2 adducts (5), (6) and (9) resulting from an “ene” reaction of the initially forced cycloadducts. The obtention of the adducts (5) and (6) in equimolecular amounts is a good example of the non-regioselective character of the “ene” reaction. The reaction with tetracyanoethylene takes place through the olefinic substituent giving the π2 + π2 adduct (10).
The reactivity of 2-vinylindoles with dimethyl acetylenedicarboxylate
Abstract The overall rates of reaction of 1-substltuted-1- (1-methyl-2-indolyl)ethenes with dimethyl acetylenedicarboxylate are considerably lower than those of the corresponding 2-vinyl- pyrroles. Steric interaction between the N-methyl group on the indole ring and the 1-substituent on the ethenyl group prevents the diene system adopting a coplanar cisoid configuration and, thereby, inhibits the π4 + π2 cycloaddition reaction of the system with dimethyl acetylenedicarboxylate. Under such conditions, the indolylethene preferentially undergoes a Michael addition reaction at the 3-position. The π4 + π2 cycloaddition reaction is promoted at elevated temperatures. No evidence was found for a Co…
Oxidation of aminodiols mediated by homogeneous and heterogeneous TEMPO
The conversion of amino diols to aminohy- droxy acids by oxidation of the primary hydroxy group mediated by homogeneous and heterogeneous TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl radi- cal) is reported. The synthesis uses NaOCl as primary oxidant and TEMPO, either dissolved in the homoge- neous phase or entrapped in a sol-gel matrix, as cata- lytic mediator. Homogeneous TEMPO is suitable for the oxidation of aliphatic methylamino diols, while the hybrid organic-inorganic silica sol-gel catalysts are more selective mediators for the oxidation of ben- zylic amino diols like the potent antibiotic chloram- phenicol which, under homogeneous conditions, are unselectively oxidized to benzoic ac…