23517-42-2

Usage

Compound class

Oximes (organic compounds)

Physical appearance

Colorless to light yellow liquid

Odor

Faint

Solubility

Insoluble in water

Common uses

Organic synthesis, reagent in chemical reactions, pharmaceutical and agrochemical industries

Safety concerns

Potential allergen and irritant, caution advised when handling

Upstream product

• 25695-90-3 [(E)-(2-nitrobut-1-en-1-yl)benzene] 
• 71-43-2 benzene 
• 673-32-5 1-Phenylprop-1-yne 
• 93-55-0 1-phenyl-propan-1-one 

Downstream Products

• 125803-12-5 3-[1-Phenyl-prop-(E)-ylideneaminooxy]-propionic acid ethyl ester 
• 2698-79-5 (R)-N-(1-phenylpropyl)acetamide 
• 125402-82-6 (E)-1-phenylpropanone O-benzyl oxime 
• 75039-34-8 (E)-propiophenone O-methyl oxime 
• 1051939-35-5 2-methyl-1-phenyl-pent-4-en-1-one oxime 
• 46165-47-3 5-ethyl-1-phenyl-1H-tetrazole 
• 93-55-0 1-phenyl-propan-1-one 
• 17799-61-0 3,4-dimethyl-2,5-diphenyl-1H-pyrrole 
• 620-71-3 N-(phenyl)-2-methylacetamide 
• 15545-80-9 1,1,3,3-tetraphenyldisiloxane 
• 2941-20-0 1-phenylpropylamine 
• 622-80-0 N-propylaniline 
• 24388-23-6 2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxoborole 

Relevant academic research and scientific papers

Transformations of Aryl Ketones via Ligand-Promoted C?C Bond Activation

The coupling of aromatic electrophiles (aryl halides, aryl ethers, aryl acids, aryl nitriles etc.) with nucleophiles is a core methodology for the synthesis of aryl compounds. Transformations of aryl ketones in an analogous manner via carbon–carbon bond activation could greatly expand the toolbox for the synthesis of aryl compounds due to the abundance of aryl ketones. An exploratory study of this approach is typically based on carbon–carbon cleavage triggered by ring-strain release and chelation assistance, and the products are also limited to a specific structural motif. Here we report a ligand-promoted β-carbon elimination strategy to activate the carbon–carbon bonds, which results in a range of transformations of aryl ketones, leading to useful aryl borates, and also to biaryls, aryl nitriles, and aryl alkenes. The use of a pyridine-oxazoline ligand is crucial for this catalytic transformation. A gram-scale borylation reaction of an aryl ketone via a simple one-pot operation is reported. The potential utility of this strategy is also demonstrated by the late-stage diversification of drug molecules probenecid, adapalene, and desoxyestrone, the fragrance tonalid as well as the natural product apocynin.

Copper-catalyzed synthesis of oxime ethers from iminoxy radical (C[dbnd]N–O[rad]) and maleimides via radical addition

An efficient Cu(II)-catalyzed radical addition of maleimides has been achieved. The identified copper catalyst enables the formation of oxime radicals (N–O[rad]) by cleaving the O–H bond in ketoximes, followed by the radical addition to N-substituted male

Stereospecific synthesis of 1,5-disubstituted tetrazoles from ketoximes via a Beckmann rearrangement facilitated by diphenyl phosphorazidate

A novel method for the stereospecific synthesis of 1,5-disubstituted tetrazoles from ketoximes via the Beckmann rearrangement was developed using diphenyl phosphorazidate (DPPA) as both the oxime activator and azide source. Various ketoximes were transformed into the corresponding 1,5-disubstituted tetrazoles with exclusive trans-group migration and no E-Z isomerization of the ketoxime. This method enables the preparation of 1,5-disubstituted tetrazoles without using toxic or explosive azidation reagents.

Enantioselective Hydrogenation of Activated Aryl Imines Catalyzed by an Iron(II) P-NH-P′ Complex

Chiral amines are key building blocks in synthetic chemistry with numerous applications in the agricultural and pharmaceutical industries. Asymmetric imine hydrogenation, particularly with iridium catalysts, is well developed. However, imine reduction still remains challenging in the context of replacing such a precious metal with a cheap, nontoxic, and environmentally friendly substitute such as iron. Here, we report that an unsymmetrical iron P-NH-P′ catalyst that was previously shown to be effective for the asymmetric hydrogenation of aryl ketones is also a very effective catalyst for the asymmetric hydrogenation of prochiral aryl imines activated with N-diphenylphosphinoyl or N-tosyl groups. The P-NH-P′ abbreviation stands for (S,S)-PPh2CHPhCHPhNHCH2CH2PiPr2. Density functional theory results suggest that, surprisingly, the NH group on the catalyst activates and orients the imine to hydride attack by hydrogen bonding to the PO or SO group on the imine nitrogen, as opposed to the imine nitrogen itself. This may explain why N-Ph and N-Bu imines are not hydrogenated.

Dichloroimidazolidinedione-Activated Beckmann Rearrangement of Ketoximes for Accessing Amides and Lactams

A novel protocol for the activation of the Beckmann rearrangement utilizing the readily available and economical geminal dichloroimidazolidinediones (DCIDs) on a substoichiometric scale (10 mol %) has been developed. A unique self-propagating mechanism for the substoichiometric dichloroimidazolidinedione-activated transformation was proposed and validated. The substrate scope of the developed protocol has been demonstrated by 23 examples with good to excellent yields (mostly 90-98%) in a short time (mostly 10-30 min), including a substrate for synthesizing the monomer of nylon-12 and a complicated steroidal substrate on a preparative scale. This research not only unveils for the first time the synthetic potential of substoichiometric amounts of dichloroimidazolidinediones in promoting chemical transformation but also offers yet another important illustration of the self-propagating cycle in the context of the Beckmann rearrangement activated by a structurally novel organic promoter.

Divergent Iron-Catalyzed Coupling of O-Acyloximes with Silyl Enol Ethers

An iron-catalyzed coupling reaction of O-acyloximes and O-benzoyl amidoximes with silyl enol ethers is reported. The protocol provides access to functionalized pyrroles, 1,6-ketonitriles, pyrrolines and imidazolines via carbon-centered radicals generated from an initially formed iminyl radical. The intramolecular cyclization and ring-opening processes of the iminyl radical take place preferentially over reactions that proceed through a 1,3-hydrogen transfer, providing insights into iron-catalyzed reactions with oxime derivatives. The cheap and environmentally friendly iron catalyst, the broad substrate scope and the functional group compatibility make this protocol useful for synthesis of valuable nitrogen-containing products.

Intermolecular cope-type hydroamination of alkenes and alkynes

(Chemical Equation Presented) Keep it simple! Intermolecular hydroamination can be achieved simply upon heating alkynes and alkenes with aqueous hydroxylamine. Alkynes react to afford oximes in good to excellent yields, and the formation of Markovnikov products is favored. A mechanism involving Cope-type hydroamination followed by bimolecular proton transfer is suggested and supported by DFT studies.

Enantioselective Strecker-type reaction of phosphinoyl ketimines catalyzed by a chiral Zr-bipyridyldiol catalyst

An enantioselective Strecker reaction of N-diphenylphosphinoyl ketimines with TMSCN employing a chiral zirconium complex formed from chiral bipyridyl diol 1 as catalyst is described. The catalytic efficiency of chiral ligand 1 with other Lewis acids was also explored. Higher yields (50-85%) with moderate to good enantioselectivities (30-80%) were achieved for a variety of N-diphenylphosphinoyl ketimines.

Mercury-catalyzed rearrangement of ketoximes into amides and lactams in acetonitrile

(Chemical Equation Presented) An acetonitrile solution of mercury(II) chloride has been found to catalyze efficiently the conversion of a diverse range of ketoximes into their corresponding amides/lactams.

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.