28570-76-5

Upstream product

• 10341-75-0 (E)-1-phenylethanone oxime 
• 100-39-0 benzyl bromide 
• 100-44-7 benzyl chloride 
• 98-86-2 acetophenone 
• 620-05-3 iodomethylbenzene 
• 2687-43-6 O-benzylhydoxylamine hydrochloride 
• 62-53-3 aniline 
• 177750-80-0 1-Benzenesulfonyl-ethanone O-benzyl-oxime 
• 622-33-3 N-benzyloxyamine 
• 585-71-7 (1-bromoethyl)benzne 
• 613-91-2 acetophenone oxime 

Downstream Products

• 2627-86-3 (S)-1-phenyl-ethylamine 
• 3886-69-9 (R)-1-phenyl-ethyl-amine 
• 120254-57-1 O-benzyl-N-(1-phenylethyl)hydroxylamine 
• 33290-12-9 (1S)-N-1-Phenethyl-3-hydroxy-2,2-dimethylpropanamide 
• 14185-43-4 (R)-(1-phenylethyl)-carbamic acid ethyl ester 
• 1233200-21-9 (Z)-acetophenone O-benzyloxime 
• 1201946-28-2 (E)-1-(o-tolyl)ethanone O-benzyl oxime 
• 613-91-2 acetophenone oxime 
• 13280-20-1 1-phenylethanimine 
• 108-88-3 toluene 
• 100-51-6 benzyl alcohol 
• 92-52-4 biphenyl 
• 100-52-7 benzaldehyde 
• 103-29-7 1,1'-(1,2-ethanediyl)bisbenzene 

Relevant academic research and scientific papers

Photocatalyzed Triplet Sensitization of Oximes Using Visible Light Provides a Route to Nonclassical Beckmann Rearrangement Products

Oximes are valuable synthetic intermediates for the preparation of a variety of functional groups. To date, the stereoselective synthesis of oximes remains a major challenge, as most current synthetic methods either provide mixtures of E and Z isomers or furnish the thermodynamically preferred E isomer. Herein we report a mild and general method to achieve Z isomers of aryl oximes by photoisomerization of oximes via visible-light-mediated energy transfer (EnT) catalysis. Facile access to (Z)-oximes provides opportunities to achieve regio- and chemoselectivity complementary to those of widely used transformations employing oxime starting materials. We show an enhanced one-pot protocol for photocatalyzed oxime isomerization and subsequent Beckmann rearrangement that enables novel reactivity with alkyl groups migrating preferentially over aryl groups, reversing the regioselectivity of the traditional Beckmann reaction. Chemodivergent N- or O- cyclizations of alkenyl oximes are also demonstrated, leading to nitrones or cyclic oxime ethers, respectively.

Metal-Free Transformation of Sulfonyl Oxime Ethers with Amines to Oxime Ethers

Sulfonyl oxime ethers undergo facile radical substitutions with various amines to yield the corresponding oxime ethers. An efficient arylation of sulfonyl oxime ethers was accomplished under ambient temperature and metal-free conditions, with a wide range of functional group tolerance. Mechanistic investigations indicate that a phenyl radical is involved in the catalytic cycle.

Base-promoted aromatic [3,3] sigmatropic rearrangement of N-acyl-O-arylhydroxylamine derivatives

The base-promoted aromatic [3,3] sigmatropic rearrangement of N-acyl-O-arylhydroxylamines giving α-(2-hydroxyphenyl)amides was successfully demonstrated. The substrates were prepared from N-substituted hydroxylamines by N-acylation followed by copper(I)-mediated O-arylation with boronic acids. Treatment of the substrates with lithium hexamethyldisilazide (LiHMDS) in THF at 0 °C to room temperature generated the corresponding amide enolates. The aromatic [3,3] rearrangement of the enolates provided the desired products in moderate to good yields. A crossover experiment produced only intramolecular products and clarified that the reaction proceeds via the aromatic [3,3] sigmatropic rearrangement, not a bond-cleavage–recombination process. Our method is a formal α-arylation of amides.

Palladium-catalyzed C-H activation/C-C cross-coupling reactions: Via electrochemistry

Palladium-catalyzed C-H activation/C-C cross-coupling reactions typically require stoichiometric chemical oxidants and exogenous ligands. However, there are significant disadvantages associated with the use of traditional stoichiometric oxidants. To overcome these issues, we have developed an electrochemical strategy to achieve methylation and acylation.

Bromotyrosine alkaloids from the Australian marine sponge Pseudoceratina verrucosa

Two new bromotyrosine alkaloids, pseudoceralidinone A (1) and aplysamine 7 (2), along with three known compounds were isolated from the Australian sponge Pseudoceratina verrucosa. Their structures were characterized by NMR and MS data and the synthetic ro

Metal-Free 2,2,6,6-tetramethylpiperidin-1-yloxy radical (TEMPO) catalyzed aerobic oxidation of hydroxylamines and alkoxyamines to oximes and oxime ethers

TEMPO-Mediated oxidation of hydroxylamines (=hydroxyamines) and alkoxyamines to the corresponding oxime derivatives is reported (TEMPO=2,2,6,6-tetramethylpiperidin-1-yloxy radical; Scheme 2). These environmentally benign oxidations proceed in good to excellent yields (Table 1). For alkoxyamines, oxidation to the corresponding oxime ethers can be performed by using dioxygen as a terminal oxidant in the presence of 5-10 mol-% of TEMPO or 4-substituted derivatives thereof as a catalyst (Scheme 3 and Table 2). Importantly, benzyl bromides can directly be transformed to oxime ethers via in situ alkoxyamine formation by a nucleophilic substitution followed by TEMPO-mediated oxidation (Scheme 4 and Table 3). Copyright

Enantioselective reduction of ketoxime ethers with borane-oxazaborolidines and synthesis of the key intermediate leading to (S)-rivastigmine

The reduction of representative alkyl aryl (E)-ketoxime O-benzyl ethers with borane catalyzed by terpene oxazaborolidines, derived from (1R)-nopinone and (1R)-camphor, gave the corresponding amines with 82-99% ee. Oxazaborolidines derived from (1S)-2-carene and (1S)-3-carene were less selective. (S)-1-(3-Methoxyphenyl)ethanamine (94% ee) the key intermediate in the synthesis of (S)-rivastigmine, was obtained by the reduction of (E)-1-(3-methoxyphenyl) ethanone O-benzyl oxime with borane/oxazaborolidine generated from (S)-valinol.

CATALYTIC ASYMMETRIC SYNTHESIS OF PRIMARY AMINES VIA BORANE REDUCTION OF OXIME ETHERS USING SPIROBORATE ESTERS

Asymmetric reduction of arylalkyl and pyridylalkyl ketoxime ether with borane catalyzed by several chiral spiroborates derived from non-racemic 1,2-amino alcohols are presented. Complete conversion of oxime to primary amine is highly dependant of the catalyst, source and amount of borane and temperature. The conversion and enantioselectivity is determined by the benzylic substitution of the oxime. After optimization, a catalyst derived from diphenyl valinol could, successfully, afford primary amines with good yield and enantioselectivity up to 99% ee. Using the developed methodology, other related non-racemic primary pyridyl alkyl methanamines were also prepared in high chemical yield and excellent enantioselectivity.

Asymmetric synthesis of primary amines via the spiroborate-catalyzed borane reduction of oxime ethers

The enantioselective borane reduction of O-benzyloxime ethers to primary amines was studied under catalytic conditions using the spiroborate esters 5-10 derived from nonracemic 1,2-amino alcohols and ethylene glycol. Effective catalytic conditions were achieved using only 10% of catalyst 5 derived from diphenylvalinol in dioxane at 0°C resulting in complete conversion to the corresponding primary amine in up to 99% ee.

Asymmetric reduction of oxime ethers promoted by chiral spiroborate esters with an O3BN framework

Enatioselective reduction of oxime ethers promoted by chiral spiroborate esters with an O3BN framework is reported for the first time. In the presence of (R,S)-1, 11 aralkyloxime ethers are reduced by borane-THF at 0-5 °C to give (S)-1-aralkylamine in high yield and excellent enatiomeric excess (up to 98% ee). Influence of reaction conditions on the enantioselectivity of the reduction is investigated, and a possible mechanism of the catalytic reduction is suggested.