105207-76-9Relevant academic research and scientific papers
Synthesis of 3,6-Dihydro-2H-[1, 2]-Oxazines from Nitroarenes and Conjugated Dienes, Catalyzed by Palladium/Phenanthroline Complexes and Employing Phenyl Formate as a CO Surrogate
EL-Atawy, Mohamed A.,Formenti, Dario,Ferretti, Francesco,Ragaini, Fabio
, p. 4707 - 4717 (2018/09/25)
Palladium/phenanthroline catalyzed reduction of nitroarenes by in situ-generated carbon monoxide, from the decomposition of phenyl formate, affords the corresponding nitrosoarenes. The latter are trapped by conjugated dienes to give the corresponding 3,6-dihydro-2H-[1, 2]-oxazines (hetero Diels-Alder adducts). Many functional groups are well tolerated. Yields are higher than those obtainable by any previously reported method, including the direct reaction of the diene with the pure nitrosoarene. The reaction can be performed in a single standard glass pressure tube, without the need for autoclaves or high-pressure CO lines.
Synthesis of oxazines and N-arylpyrroles by reaction of unfunctionalized dienes with nitroarenes and carbon monoxide, catalyzed by palladium-phenanthroline complexes
Ragaini, Fabio,Cenini, Sergio,Brignoli, Daniela,Gasperini, Michela,Gallo, Emma
, p. 460 - 466 (2007/10/03)
The reaction between an unfunctionalized conjugated diene and a nitroarene under CO pressure and at 100 °C, catalyzed by [Pd(Phen)2][BF4]2 (Phen = 1,10-phenanthroline), affords the corresponding hetero-Diels -Alder adduct (oxazine) in up to 91% yields in one pot. If the reaction mixture is then heated to 200 °C, the oxazines are converted into the corresponding N-arylpyrroles in good yields. Pressures as low as 5 bar can be employed, and 0.08% catalyst is sufficient to effect the transformation. The reaction can be equally run by employing the nitroarene or the diene as limiting agent and works well for nitroarenes bearing either electron-withdrawing or mildly electron-donating substituents. A moderate steric hindrance on the nitroarene (o-methyl) is well tolerated, but 1,4-disubstituted-1,3-dienes are not suitable substrates.
A molybdenum-catalyzed oxidative system forming oxazines (hetero-Diels-Alder adducts) from primary aromatic amines, hydrogen peroxide, and conjugated dienes
Moller, Eval Rud,Jorgensen, Karl Anker
, p. 5770 - 5778 (2007/10/03)
The development of a new molybdenum-catalyzed procedure for the formation of oxazines-hetero-Diels-Alder adducts - from primary aromatic amines, hydrogen peroxide, and conjugated dienes is presented. The method is based on a molybdenum-peroxo complex, which in the presence of hydrogen peroxide as the terminal oxidant selectively catalyzes the oxidation of primary aromatic amines to the corresponding dienophilic nitroso compounds. The molybdenum-peroxo catalyst is under the present reaction conditions not reactive toward conjugated dienes and substituents attached to the aromatic nuclei of the primary aromatic amines. Several oxazines are synthezised following this new procedure using primary aromatic amines having either electron-withdrawing or electron-donating substituents and 1,3-cyclohexadiene as the standard diene. The scope of the new procedure is also demonstrated by the preparation of several oxazines using different alkyland phenyl-substituted conjugated dienes and 4-chloroaniline as precursor for the dienophile. Moderate diastereomeric excesses are found when the reaction is carried out with 1-(2-aminophenyl)-ethanol and 1,3-cyclohexadiene or (E)-1-phenyl-1,3-butadiene. The stereochemical and electronic factors governing the reaction course are briefly discussed.
