Phenyl oxaziridine

An investigation of acylaziridines was carried out by comparison of IR, NMR and MS data and included some 1,2-dibenzoylaziridines as well as 2-p-nitrobenzoyl-3-phenyl-oxaziridine (68IZV1530). Amide conjugation in acylated nitrogen-containing three-membered rings is weaker than in open chain acid amides. 

In some cases acid amide formation was observed on attempted deprotonation at oxaziridine ring carbon. 2-r-Butyl-3-(4 -nitrophenyl)oxaziridine (67) was converted to the anion of acid amide (68) by sodium amide (69TL3887), while 2-(4 -nitrobenzoyl)-3-phenyl-oxaziridine (69) afforded the diacylimide (70) by addition of cyclohexylamine to its benzene solution at room temperature (67CB2593). 

In order to optimize oxidation conditions of diethyl(2-methylpyrrolidine-2-yl) phosphonate into the corresponding nitrone, a comparative analysis of the action of various oxidants such as H2O2, m-CPBA, Oxone, 2-phenylsulfonyl-3-phenyl-oxaziridine (PSPO), DMD, and A-methylrnorpholine /V-oxide in the presence of a catalytic quantity of tetrapropylammonium perruthenate (NMO/TPAP) has been made (92). 

TABLE 4-19. Diasteroselective Hydroxylation of Chiral Carboximide Sodium Enolates Using 2-(Phenylsulfonyl)-3-Phenyl-Oxaziridine (141) in THF at — 78°C... 

The anisyl group was used since the phenyl oxaziridines simply isomerized to nitrones upon acid treatment. The yields were modest (30-40%), but the products were optically pure. A similar method was used to make 5-A -hydroxy-L-arginine and 6-A -hydroxy-L-ornithine, and the optically active hydroxylamine precursor of dopastin. ... 

Table 11 Epoxidation of alkenes using 2-(phenylsulfonyl)-3-(p-nitro-phenyl)-oxaziridine (63b) at 60 °C in CHCl3.a...

Triethoxy-l,2A5-oxaphospholene (112) reacts at room temperature with 2-(p-tolyl)-3-phenyl-oxaziridine (63d) to give a /Miydroxy-y-ketophosphate (113) in 82% yield (Equation (26)) (91TL5313). It seems likely that an oxirane intermediate is initially formed which rearranges on work-up to (113). Asymmetric oxidation with (+ )-[(8,8-dichlorocamphoryl)sulfonyl]oxaziridine (74) gave (113) in 49% ee and 88% isolated yield. The absolute configuration of (113) was not established. 

Multigram quantities of A-methoxycarbonyl-3-phenyloxaziridine (53a) and A-Boc-3-phenyl-oxaziridine (53b) are produced by carefully controling the oxidation of the corresponding imines with buffered Oxone in biphasic media (Equation (49)) <91CC435,93JOC4791). The principle product is amide (190) if the oxidation is carried out at room temperature or with MCPBA. 

Durch 2-Aroyl-3-phenyl-oxaziridin mit Elektronenacceptor-Substituenten im Aryl-Rest gelingt die elektrophile Aminierung von 5-Hydroxy-3-methyl-l-phenyl-1 H-pyrazol in 4-Position1618 ... 

In the selenium series, methyl phenylselenide in chtoroform at 25°C upon portionwise treatment with 1 mole of 2-benzenesulphonyl-3-(4-nitro-phenyl)oxaziridine and reaction for 1 min. only, gave the selenoxide in 97% yield (ref. 183). 

The asymmetric hydroxylation of A-non-substituted ethyl 2-carbamoyl-2-phenylacetate in THF was mediated by Davis oxaziridine, 2-(benzenesulfonyl)-3-phenyl-oxaziridine as oxidant in the presence of a combination of rare-earth metal alkoxide Pr(OPr )3 and the ligand A-((S)-l-(2-hydroxyphenylcarbamoyl)-2-methylpropyl)-2-hydroxybenzamide as catalyst afforded enantioenriched (68-92% ee) (R)-ethyl 2-carbamoyl-2-hydroxy-2-phenylacetate (yield 39-96%) with a densely... 

Phenyl isocyanate reacts with (82) to form (83) by ring enlargement (74JOC948). Reaction of oxaziridines with diphenylketene proceeds less obviously. Isolated products (84) and (85) contain only the R—N group of the starting material (69TL263). 

Oxaziridine, 2-t-hutyl-3-(4-nitrophenyl)-hydrolysis rate constant, 7, 207 (71JCS(B)778) Oxaziridine, 2-t-hutyl-3-phenyl-7, 205 (57JOC1263)... 

Singlet phenylnitrene, and hence /V,A -diethyl-3//-azcpin-2-amines, e. g. 102, can be generated by the thermolysis of A,-phenyl-Af,<9-bis(trimcthylsi]yl)hydroxylamine (100) in the presence of dialkylamines the reaction fails, however, with arylamines.210 Photofragmentation of the spiro oxaziridine 101 in diethylamine solution also produces the 3//-azepine 102,2,1 and an oxaziridine intermediate is probably involved in the formation, in low yield (1 %), of azepine 102 by the photolysis of A/,A( -diarylbenzoquinonc diimine A/,A/ -dioxides in benzene/die-thylamine solution.212... 

A further stage of reduction is reached when an oxaziridine (32) opens in the presence of phenyl isocyanate. This can be accomplished [Eq. (34)] in a sealed tube at 85° in benzene to give a 94% yield of a... 

In 6-methyl- and 6-phenylphenanthridine 5-oxide (181 R = CH3, Ph), rearrangement of the intermediate oxaziridine is accompanied by methyl or phenyl migration, and 5-methyl- and 5-phenyl-6-(5 )-phenanthridinones (182 R = CH3, Ph) are isolated in high yield on irradiation in ethanol,156 In benzene solution, however, the photolysis is more complex,156 and the principal products of irradiation of 6-phenylphenanthridine 5-oxide are 2-benzamido-2 -hydroxybi-phenyl, 6-phenylphenanthridine, and 5-phenyl-6-(5i/)-phenanthri-done. 

Migration accompanying the cleavage of an oxaziridine is also involved in the rearrangement in high yield of 2-benzoyl-3-phenyl-quinoxaline 1,4-dioxide (183) to the benzimidazolone (184) on photolysis in methanol.167... 

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