43052-01-3

Upstream product

• 15875-74-8 N-(4-methoxybenzylidene)-2-methylpropan-2-amine 
• 15875-74-8 (E)-tert-butyl[(4-methoxyphenyl)methylidene]amine 
• 123-11-5 4-methoxy-benzaldehyde 
• 75-64-9 tert-butylamine 

Downstream Products

• 19486-73-8 N-tert-butyl-4-methoxybenzamide 
• 40117-28-0 N-(4-methoxy)benzylidene-t-butylamine N-oxide 
• 123-11-5 4-methoxy-benzaldehyde 
• 1193-82-4 racemic methyl phenyl sulfoxide 
• 15875-74-8 N-(4-methoxybenzylidene)-2-methylpropan-2-amine 
• 1253786-06-9 2-tert-butyl-3-(4-methoxyphenyl)-2,3-dihydrobenzo[d]isoxazole 
• 1253786-19-4 2-tert-butyl-3-(4-methoxyphenyl)-5,6-dimethyl-2,3-dihydrobenzo[d]isoxazole 
• 1253786-22-9 2-tert-butyl-1-(4-methoxyphenyl)-1,2-dihydronaphtho[1,2-d]isoxazole 

Relevant academic research and scientific papers

Weak base-promoted selective rearrangement of oxaziridines to amidesviavisible-light photoredox catalysis

The selective rearrangement of oxaziridines to amidesviaa single electron transfer (SET) pathway is unexplored. In this study, we present a weak base-promoted selective rearrangement of oxaziridines to amidesviavisible-light photoredox catalysis. The developed method shows excellent functional group tolerance with a broad substrate scope and good to excellent yields. Furthermore, control experiments and density functional theory (DFT) calculations are performed to gain insight into the reactivity and selectivity.

Enantio-and diastereoselective oxidation of N-alkylimines using chiral-bromonitriles and hydrogen peroxide system

Chiral-bromonitriles were prepared with good chemical and optical yields starting from natural-amino acids by dehydrating the corresponding α-bromoamides with thionyl chloride. The combined system-bromonitriles/ hydrogen peroxide was examined for the enantio-and diastereoselective oxidation of N-alkylimines in basic media at room temperature. The oxidation of N-tertiobutylarylimines leads to optically active oxaziridines with moderate enantiomeric excess. However, the oxidation of (S)-1-phenylethylarylimines affords the corresponding oxaziridines with good diasteromeric excess up to 97/3 as proved by gaseous-phase chromatography.

Synthesis of dihydrobenzisoxazoles by the [3 + 2] cycloaddition of arynes and oxaziridines

Dihydrobenzisoxazoles are readily prepared in good yields by the [3 + 2] cycloaddition of oxaziridines and arynes. The reaction involves an unusual cleavage of the C-O bond of the oxaziridine and tolerates a variety of substituents on the oxaziridine and the o-(trimethylsilyl)aryl triflate to form aryl-, heteroaryl-, alkyl-, and naphthyl-substituted dihydrobenzisoxazoles. The resulting halogen-substituted dihydrobenzisoxazoles are readily elaborated to more complex products using palladium-catalyzed crossing-coupling processes.

[Bmim]BF4-immobilized rhenium-catalyzed highly efficient oxygenation of aldimines to oxaziridines using solid peroxides as oxidants

Various rhenium-based catalysts immobilized in [bmim]BF4 were found to be efficient for oxygenation of various aldimines to the corresponding oxaziridines in excellent yields under mild conditions using solid peroxides like UHP, SPC and SPB as oxidants. Among the various rhenium-based catalysts studied, MTO was found to be most efficient. The reusability and recyclability of MTO immobilized in [bmim]BF4 was established by using it for three subsequent cycles for oxygenation of benzylidine-tert-butylamine using UHP as oxidant.

An environmentally friendly oxidation system for the selective oxygenation of aldimines to oxaziridines with anhydrous TBHP and alumina-supported MoO 3 as a recyclable heterogeneous catalyst

A highly efficient and selective protocol for the oxygenation of various aldimines to oxaziridines, which proceeds in excellent yields with enhanced selectivity by using alumina-supported M0O3 as a recyclable heterogeneous catalyst and anhydrous TBHP as the ultimate oxidant, is described. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Sulfonic peracids - III. Heteroatom oxidation and chemoselectivity

We have investigated the p-toluenesulfonic peracid (2) generated in situ in the oxidation of different types of compounds containing nitrogen and/or sulfur. The sulfonic peracid 2 shows a remarkable chemoselectivity characterized by a preferred oxidation of sulfides to the sulfones in the presence of amines or olefins and a strong dependence on the nature of the amine in the competitive oxidation of olefins and amines.

Oxidation of Imines to Oxaziridines catalysed by Transition Metal Complexes using Molecular Oxygen as the Terminal Oxidant

The metal-catalysed oxidation of imines using molecular oxygen as the terminal oxidant and aldehydes as co-reductants has been studied.Different transition metal complexes have been tested as catalysts and it is found that cobalt complexes can catalyse the selective oxidation of imines to oxaziridines.The cobalt-catalysed oxidation of imines to oxaziridines is dependent on the aldehyde used as co-reductant; thus, the presence of aliphatic aldehydes leads to a smooth oxidation, whilst in the presence of aromatic aldehydes there was no reaction.The oxidation proceeds well for imines with aliphatic and aromatic substituents attached to the nitrogen and carbon atom, respectively.The electronic nature of the oxygen atom transferred in these reactions, investigated using thianthrene 5-oxide as a probe, was found to be electrophilic in character.The mechanistic aspects of the cobalt-catalysed oxidation of imines to oxaziridines, probably involving a peroxyacyl cobalt intermediate, are discussed.

Imines and Derivatives. Part 24. Nitrone Synthesis by Imine Oxidation using either a Peroxyacid or Dimethyldioxirane

The oxidation of N-alkyl imines by m-chloroperoxybenzoic acid to yield nitrones was facilitated by (i) the presence of C-aryl substituents, (ii) steric inhibition of attack at the imino C-atom, (iii) electron donating para-substituents on the C-aryl substituent, (iv) non-hydroxylic solvents, (v) optimal conjugation between C-aryl substituents and the imino group, and (vi) less bulky N-alkyl groups. The oxidation of N-alkyl imines by dimethyldioxirane (DMD) in dichloromethane-acetone solution yielded nitrones without evidence of oxaziridine formation.The yields of isolated nitrones were higher for C,C-diaryl imines and for imines bearing less bulky N-alkyl substituents.N-H substituted ketimines were found to yield oximes after reaction with dimethyldioxirane.

Rearrangement Reactions of Oxaziridines to Nitrones. X-Ray Crystal and Molecular Structure of N-t-Butyl-α(o-hydroxyphenyl)nitrone

Substituted N-benzylidene-t-butylamines are oxidized with m-chloroperoxybenzoic acid to oxaziridines which can rearrange to the corresponding nitrones when electron-donating groups are present in the phenyl ring.The oxaziridine-to-nitrone rearrangement, which has been considered as a 'pseudo-abnormal' reaction, can also be catalysed by Lewis acids.It has been found that the rearrangement of 2-t-butyl-3-(o-hydroxyphenyl)oxaziridine to the corresponding nitrone is of first order.The rearrangement has been investigated for different substituents in the phenyl ring, andin the case of 2-t-butyl-3-phenyloxaziridine substituted in the ortho position with electron-donating groups it has been found that the presence of protons of a Lewis acid is necessary.An X-ray structure of α-(o-hydroxyphenyl)-N-t-butylnitrone shows strong hydrogen bonding between the nitrone oxygen and the hydrogen in the hydroxy group.The oxaziridine-to-nitrone rearrangement is also analysed from a theoretical point of view using ab initio calculations.A Mulliken-population analysis of the C-O and N-O bonds in the oxaziridine ring for para-substitued 2-t-butyl-3-phenyloxaziridines shows a reduction of the C-O bond population when an electron-donating group is present in the para position of the phenyl ring compared with an electron-withdrawing group; the N-O bond populations show the reverse picture.A state-correlation diagram for the oxaziridine-to-nitrone rearrangement is also presented and the experimental and theoretical results support each other.

Oxidation of Imines to Nitrones by the Permanganate Ion

A series of imines have been oxidized to nitrones in reasonable yields with the permanganate ion under phase-transfer conditions.The influence of the amount of permanganate, solvents, phase-transfer catalysts, and acidity of the aqueous phase on the reaction course have been investigated.It has been found that the presence of water is necessary for the formation of the nitrone.The best phase-transfer catalysts are quaternary ammonium salts with long aliphatic carbon chains.The mechanism for the permanganate oxidation of imines to nitrones is discussed from a frontier orbital point of view.It is suggested that the reaction proceeds via an interaction of the oxygen ligands in the permanganate ion to carbon and nitrogen in the imine.The electronic and geometrical structures of the permanganate-imine complex are discussed.