19300-92-6

Upstream product

• 52217-42-2 (1-chloro-cyclopentyl)-phenyl ketone 
• 56345-97-2 1-benzoyl-1-(trimethylsiloxy)-cyclopentane 
• 5425-44-5 2-Phenyl-[1,3]dithiane 
• 5422-88-8 phenyl cyclopentyl ketone 
• 100-47-0 benzonitrile 
• 6740-66-5 (1-bromocyclopentyl)(phenyl)methanone 
• 120-92-3 cyclopentanone 
• 25438-35-1 1-[(trimethylsilyl)oxy]cyclopentanecarbonitrile 
• 100-59-4 phenylmagnesium chloride 
• 613-90-1 benzoyl cyanide 

Downstream Products

• 135095-89-5 (1S,2R)-1-phenyl-1,2-cyclohexanediol 
• 34281-90-8 (1S,2S)-1-phenyl-1,2-cyclohexanediol 
• 4829-02-1 (S)-(+)-2-hydroxy-2-phenylcyclohexanone 
• 470480-22-9 3,4-diphenyl-1-oxa-spiro[4,4]non-3-en-2-one 
• 4829-02-1 2-hydroxy-2-phenylcyclohexanone 

Relevant academic research and scientific papers

1,5,7-Triazabicyclo[4.4.0]dec-5-ene Enhances Activity of Peroxide Intermediates in Phosphine-Free α-Hydroxylation of Ketones

The critical role of double hydrogen bonds was addressed for the aerobic α-hydroxylation of ketones catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), in the absence of either a metal catalyst or phosphine reductant. Experimental and theoretical investigations were performed to study the mechanism. In addition to initiating the reaction by proton abstraction, a more important role of TBD was revealed, that is, to enhance the oxidizing ability of peroxide intermediates, allowing DMSO to be used rather than commonly used phosphine reductants. Further characterizations with nuclear Overhauser effect spectroscopy (NOESY) confirmed the presence of double hydrogen bonds between TBD and the ketone, and kinetic studies suggested the attack of dioxygen on the TBD-enol adduct to be the rate-determining step. This work should encourage the application of TBD as a catalyst for oxidations.

Catalytic Asymmetric Acyloin Rearrangements of α-Ketols, α-Hydroxy Aldehydes, and α-Iminols by N, N′-Dioxide-Metal Complexes

A highly enantioselective acyloin rearrangement of cyclic α-ketols has been developed with a chiral Al(III)-N,N′-dioxide complex as catalyst. This strategy provided an array of optically active 2-acyl-2-hydroxy cyclohexanones in moderate to good yields with high enantioselectivities. The asymmetric isomerizations of acyclic α-hydroxy aldehydes and α-iminols were achieved as well under modified conditions, affording the corresponding chiral α-hydroxy ketones and α-amino ketones in moderate results. Moreover, further transformations of product to enantioenriched diols were carried out.

Α - hydroxy ketone compound low priced high-efficient synthetic method

The invention discloses a cheap and efficient synthesis method of an alpha-hydroxyketone compound. The synthesis method is characterized in that a carbonyl compound undergoes an oxidation hydroxylation reaction at 10-120DEG C under normal pressure with iodine simple substance, N-bromosuccimide, copper bromide, bromine simple substance, hydrogen bromide, N-iodosuccimide or hydrogen iodide as a catalyst, sulfoxide as an oxidant, water or sulfoxide as a hydroxy source and sulfoxide, ethyl acetate, N,N-dimethyl formamide, acetonitrile, toluene, 1,4-dioxane, 1,2-dichloroethane, tetrahydrofuran or H2O as a solvent, and converts into the alpha-hydroxyketone compound in a high selectivity manner. Compared with traditional synthesis methods, the method disclosed in the invention has the advantages of simple operation, high yield, simple conditions, easy purification, small waste discharge amount, simple reaction apparatus, and easy industrial production. The method has wide applicability and can be used for synthesizing various alpha-hydroxyketone compounds.

I2- or NBS-catalyzed highly efficient α-hydroxylation of ketones with dimethyl sulfoxide

An efficient method for the direct preparation of high synthetic valuable α-hydroxycarbonyls is described. The simple and readily available I2 or NBS was used as catalyst. DMSO acts as the oxidant, oxygen source, and solvent. A diverse range of tertiary Csp3-H bonds as well as more challenging secondary Csp3-H bonds could be hydroxylated in this transformation. The reaction is mild, less toxic and easy to perform.

Highly efficient C-H hydroxylation of carbonyl compounds with oxygen under mild conditions

A transition-metal-free Cs2CO3-catalyzed α-hydroxylation of carbonyl compounds with O2 as the oxygen source is described. This reaction provides an efficient approach to tertiary α-hydroxycarbonyl compounds, which are highly valued chemicals and widely used in the chemical and pharmaceutical industry. The simple conditions and the use of molecular oxygen as both the oxidant and the oxygen source make this protocol very environmentally friendly and practical. This transformation is highly efficient and highly selective for tertiary C(sp3)-H bond cleavage. OH, so simple! A transition-metal-free Cs2CO 3-catalyzed α-hydroxylation of carbonyl compounds with O 2 provided a variety of tertiary α-hydroxycarbonyl compounds (see scheme; DMSO=dimethyl sulfoxide), which are widely used in the chemical and pharmaceutical industry. The simple conditions and the use of molecular oxygen as both the oxidant and the oxygen source make this protocol very efficient and practical.

A dinuclear palladium catalyst for α-Hydroxylation of carbonyls with O2

A chemo- and regioselective α-hydroxylation reaction of carbonyl compounds with molecular oxygen as oxidant is reported. The hydroxylation reaction is catalyzed by a dinuclear Pd(II) complex, which functions as an oxygen transfer catalyst, reminiscent of an oxygenase. The development of this oxidation reaction was inspired by discovery and mechanism evaluation of previously unknown Pd(III)-Pd(III) complexes.

Dihydroquinolines as novel n-NOS inhibitors

Dihydroquinolines have been synthesized and have been shown to be potent n-NOS inhibitors. Selectivity versus e-NOS was increased to approximately 100-fold through appropriate substitution at the benzene ring.

Reductive Coupling of Benzoyl Cyanide and Carbonyl Compounds by Aqueous Ti(III) Ions. A New Convenient and Selective Access to the Less Stable Mixed Benzoins

The reactive species formed by the Ti(III) ion reduction of benzoyl cyanide (1) adds to the C-atom of carbonyl compounds 2 under simple experimental conditions.The intermediate 1,2-diols 3 are smoothly converted, without isolation, into the less thermodynamically stable mixed benzoins 4, which are not accessible by the classical benzoin condensation.The possible mechanisms involved in the reaction are discussed.

HYDROLYSIS OF KETOL TRIMETHYLENEDITHIOACETALS. ATTEMPTED SYNTHESIS OF YASHABUSHIKETOL

Thallium(III) trifluoroacetate has been shown to cleave dithianes which contain hydroxy functions that other reagents fail.Hydrolysis of a direct precursor of yashabushiketol led to tetrahydro-γ-pyrones, however.

Diels-Alder Approach to Bicyclic α-Hydroxy Ketones. Facile Ketol Rearrangements of Strained α-Hydroxy Ketones

The trimethylsiloxy-substituted dienophiles 1-benzoyl-1-(trimethylsiloxy)ethylene, 6, 1-carbomethoxy-1-(trimethylsiloxy)ethylene, 12, and 1-acetyl-1-(trimethylsiloxy)ethylene, 4, all reacted with cyclopentadiene to give adducts in which the carbonyl containing substituent of the major product occupied the exo position, in violation of the Alder rule.Desilylation of the Diels-Alder adducts of cyclopentadiene with 4 and 6 led to ring-expanded ketol rearrangement products on silica gel chromatography.This facile rearrangement was attributed to relief of strain in the star ting α-hydroxy ketone.Equilibration studies showed that in the rearranged 2-hydroxy-2-substituted bicyclooctan-3-one systems 24 and 30, the more stable isomer is the one in which the phenyl or methyl substituent is in the axial position.The presence of a strong intramolecular hydrogen bond of the equatorial hydroxyl group with the carbonyl group accounts for the greater stability of 24 and 30.Acetolysis of endo-2-benzoyl-exo-2-norbornyl mesylate, 2, occurred readily, giving mainly the rearranged product of internal return, 1-benzoyl-exo-norbornyl mesylate, 38.The high reactivity of 2 relative to the endo analogue and the α-H analogue was attributed to some transition-state carbonyl conjugation with the incipient α-keto cation center as well as possible neighboring ?-participation and/or steric rate enhancement.