159330-32-2

Upstream product

• 103855-80-7 α-benzylamino-isobutyric acid 
• 622-30-0 N-benzyl hydroxylalmine 
• 67-64-1 acetone 
• 102-97-6 Benzyl-isopropyl-amin 
• 29334-76-7 N-benzyl-N-isopropylhydroxylamine 

Downstream Products

• 204575-70-2 (2-Benzyl-isoxazolidin-3-yl)-acetic acid ethyl ester 
• 204575-67-7 2-(Benzyl-hydroxy-amino)-propan-2-ol 
• 204575-73-5 [(3S,4S)-2-Benzyl-4-(tert-butyl-dimethyl-silanyloxy)-isoxazolidin-3-yl]-acetic acid ethyl ester 
• 204575-72-4 [(3R,4S)-2-Benzyl-4-(tert-butyl-dimethyl-silanyloxy)-isoxazolidin-3-yl]-acetic acid ethyl ester 
• 204575-83-7 N-Benzyl-N-(2-benzyl-3,3,5-trimethyl-isoxazolidin-5-yl)-hydroxylamine 

Relevant academic research and scientific papers

Regiochemistry and mechanism of oxidation of N-benzyl-N-alkylhydroxylamines to nitrones

The oxidation of various N-(o-, m-, p-substituted benzyl)-N-alkylhydroxylamines and their dideuteriobenzyl (PhCD2) counterparts was carried out using mercury(II) oxide and p-benzoquinone (p-BQ) as oxidants. An overwhelming preference for the formation of conjugated nitrones is observed in the oxidation of N-benzyl-N-isopropylhydroxylamines. Considerable intra- and intermolecular kinetic isotope effects and negative ρ values in the Hammet plots point towards a mechanistic pathway that involves electron transfer from nitrogen to the oxidant followed by hydrogen abstraction. The conformation of unstable (E)-nitrones, which readily isomerize to the more stable (Z)-nitrones, is deduced from 1H NMR data. The E ? Z isomerization was found to be a bimolecular process. Copyright

Regioselective synthesis of nitrones by decarboxylative oxidation of N- alkyl-α-amino acids and application to the synthesis of 1-azabicyclic alkaloids

Tungstate-catalyzed oxidation of N-alkyl-2a-amino acids with 30% H2O2 solution under phase-transfer conditions gives nitrones regioselectively in good yields: Using this method, stereodivergent synthesis of (R)- and (S)-4- (t-butyldimethylsilyloxy)-1-pyrroline N-oxides ((R)-17a and (S)-17a) was achieved. In addition, (R)- and (S)-3-(t-butyldimethylsilyloxy)-1-pyrroline N-oxides ((R)-45 and (S)-45) were prepared by catalytic oxidation of the corresponding chiral pyrrolidines in a regioselective manner. These chiral cyclic nitrones, 17 and 45 are versatile intermediates for the synthesis of optically active nitrogen heterocycles, since stereoselective additions of carbon nucleophiles to these chiral nitrones can be readily performed. Typically, ZnI2-mediated addition of ketene t-butyldimethylsilyi methyl acetal (29a): to (R)-17a gave the' cis-adduct, methyl (2R,4R)-[1,4-bis(t- butyldimethylsilyloxy)pyrrolidin-2-yl]acetate (cis-30). In contrast, the addition of lithium acetylides 34 to the nitrone (R)-17a gave the trans- adducts, (2S,4R)-2-(1-alkynyl)-4-(t-butyldimethylsilyloxy)-1- hydroxypyrrolidines trans-35. These adducts are useful intermediates for syntheses of the nitrogen heterocycles (3R,5R)-1-aza-3- hydroxybicyclo[3.3.0]octane (37) and (6R,8R)-1-aza-8- hydroxybicyclo[4.30]nonane (38), respectively. The ZnI2-mediated addition of ketene silyl acetal 29a to the nitrone (R)-45 gave methyl (2S, 3R)-[1,3- bis(t-butyldimethylsilyloxy)pyrrolidin-2-yl]acetate (trans-50a), which was used for asymmetric synthesis of the Geissman-Waiss lactone ((-)-49).

Hemiaminal generated by hydration of ketone-based nitrone as an N,O-centered nucleophile in organic synthesis

Isoxazolidines that are useful precursors for β-amino acids have been prepared relying on intermolecular amino Michael addition-intramolecular S(N)2 displacement employing hydroxylamine or hydrate of ketone-based nitrone as an N- and O-centered binucleophile.

Methyltrioxorhenium-Catalyzed Oxidation of Secondary and Primary Amines with Hydrogen Peroxide

The methyltrioxorhenium-catalyzed oxidation of secondary amines and primary amines with hydrogen peroxide has been carried out. The oxidation of secondary amines afforded nitrones in good-to-excellent yield. Benzylamines were selectively oxidized to oximes, while general primary alkylamines possessing the α-C -H bond gave mixtures of oximes, nitroso dimers, and azoxy compounds.

Regiochemistry of mercury(II) oxide oxidation of unsymmetrical N,N-disubstituted hydroxylamines

Mercury(II) oxide oxidation of N,N-disubstituted hydroxylamines with the α and α' carbon atoms containing one and two hydrogen atoms, respectively, gave aldonitrones in a highly regioselective manner. Removal of the α proton is involved in the rate determining step as shown by primary kinetic isotope effect.

Tungstate-Catalyzed Decarboxylative Oxidation of N-Alkyl-α-amino Acids: An Efficient Method for Regioselective Synthesis of Nitrones

The tungstate-catalyzed oxidation of N-alkyl-α-amino acids with hydrogen peroxide under phase-transfer conditions gives the corresponding nitrones in satisfactory yield.