56705-38-5

Upstream product

• 672-65-1 (1-chloroethyl)benzene 
• 98-86-2 acetophenone 
• 101292-09-5 2-chloro-2,3-diphenyl-butane 
• 67-64-1 acetone 
• 13466-30-3 (1-phenylethylidene)hydrazine 
• 98-85-1 1-Phenylethanol 
• 28795-94-0 1,2-diphenyl-1-propanol 
• 34713-70-7 2-Phenylpropanal 
• 108-86-1 bromobenzene 
• 769-59-5 3-phenyl-butan-2-one 
• 591-51-5 phenyllithium 
• 2042-85-5 1,2-diphenylpropan-1-one 
• 75-16-1 methylmagnesium bromide 
• 917-54-4 methyllithium 

Downstream Products

• 2510-98-7 2,3-diphenyl-2-butene 
• 1857-74-5 ((2S,3S)-butane-2,3-diyl)dibenzene 
• 782-05-8 (Z)-2,3-diphenyl-2-butene 
• 782-06-9 (E)-2,3-diphenylbutene 
• 2726-21-8 2,3-diphenylbutane 
• 4613-11-0 2,3-diphenylbutane 
• 22875-84-9 2,3-diphenyl-1-butene 

Relevant academic research and scientific papers

The Stereochemistry of Condensation Reactions of (+/-)-3-Phenylbutan-2-one with Phenylmetallic Compounds as a Function of the Reagent Nucleophilicity

The influence of changing the metall and adding electrophilic catalysts or iron(III) and copper(I) salts on the stereochemical path of the nucleophilic addition of organometallics to (+/-)-3-phenylbutan-2-one is discussed.

A linear free energy correlation between solvent parameter ET(30) and stereoselectivity in the condensation of phenylmagnesium bromide with (±)-3-phenylbutanone.

A direct influence of the solvent on the RS,SR/RR,SS ratio in nucleophilic additions of phenylmagnesium bromide to (±)-3-phenylbutanone is reported.

Asymmetric Hydrogenation of Unfunctionalized Tetrasubstituted Acyclic Olefins

Asymmetric hydrogenation has evolved as one of the most powerful tools to construct stereocenters. However, the asymmetric hydrogenation of unfunctionalized tetrasubstituted acyclic olefins remains the pinnacle of asymmetric synthesis and an unsolved challenge. We report herein the discovery of an iridium catalyst for the first, generally applicable, highly enantio- and diastereoselective hydrogenation of such olefins and the mechanistic insights of the reaction. The power of this chemistry is demonstrated by the successful hydrogenation of a wide variety of electronically and sterically diverse olefins in excellent yield and high enantio- and diastereoselectivity.

Triphosgene and DMAP as Mild Reagents for Chemoselective Dehydration of Tertiary Alcohols

The utility of triphosgene and DMAP as mild reagents for chemoselective dehydration of tertiary alcohols is reported. Performed in dichloromethane at room temperature, this reaction is readily tolerated by a broad scope of substrates, yielding alkenes preferentially with the (E)-geometry. While formation of the Hofmann products is generally favored, a dramatic change in alkene selectivity toward the Zaitzev products is observed when the reaction is carried out in dichloroethane at reflux.

Bimetallic Nanoparticles in Supported Ionic Liquid Phases as Multifunctional Catalysts for the Selective Hydrodeoxygenation of Aromatic Substrates

Bimetallic iron–ruthenium nanoparticles embedded in an acidic supported ionic liquid phase (FeRu@SILP+IL-SO3H) act as multifunctional catalysts for the selective hydrodeoxygenation of carbonyl groups in aromatic substrates. The catalyst material is assembled systematically from molecular components to combine the acid and metal sites that allow hydrogenolysis of the C=O bonds without hydrogenation of the aromatic ring. The resulting materials possess high activity and stability for the catalytic hydrodeoxygenation of C=O groups to CH2 units in a variety of substituted aromatic ketones and, hence, provide an effective and benign alternative to traditional Clemmensen and Wolff–Kishner reductions, which require stoichiometric reagents. The molecular design of the FeRu@SILP+IL-SO3H materials opens a general approach to multifunctional catalytic systems (MM′@SILP+IL-func).

Aldehydes as alkyl carbanion equivalents for additions to carbonyl compounds

Nucleophilic addition reactions of organometallic reagents to carbonyl compounds for carbon-carbon bond construction have played a pivotal role in modern chemistry. However, this reaction's reliance on petroleum-derived chemical feedstocks and a stoichiometric quantity of metal have prompted the development of many carbanion equivalents and catalytic metal alternatives. Here, we show that naturally occurring carbonyls can be used as latent alkyl carbanion equivalents for additions to carbonyl compounds, via reductive polarity reversal. Such 'umpolung' reactivity is facilitated by a ruthenium catalyst and diphosphine ligand under mild conditions, delivering synthetically valuable secondary and tertiary alcohols in up to 98% yield. The unique chemoselectivity exhibited by carbonyl-derived carbanion equivalents is demonstrated by their tolerance to protic reaction media and good functional group compatibility. Enantioenriched tertiary alcohols can also be accessed with the aid of chiral ligands, albeit with moderate stereocontrol. Such carbonyl-derived carbanion equivalents are anticipated to find broad utility in chemical bond formation.

A comparative study of the McMurry reaction utilizing x, TiCl3(DME)1.5-Zn(Cu) and TiCl2 * LiCl as coupling reagents

An investigation of the reaction course and stoichiometry of the McMurry reaction of acetophenone utilizing x (THF=tetrahydrofuran), TiCl3(DME)1.5-Zn(Cu) (DME=1,2-dimethoxyethane) and TiCl2*LiCl as coupling reagents has been undertaken.The detection of 1-phenylethanol (3a) or dideutero-1-phenylethanol (3b) (Schemes 1 and 3) as hydrolysis or deuterolysis products in the early stage of reactions gave the first direct experimental evidence for the occurence of the "side-on" bonded ketones 3 and 3" as possible precursors of the pinacolates 4 and 7.This result supports the nucleophilic rather than the radical mechanism for the C-C coupling step of aromatic ketones.Contrary to the current opinion, upon refluxing TiCl3(DME)1.5-Zn(Cu) mixtures in DME, no reduction of Ti3+ to low valence Ti species could be detected.The reduction of Ti3+ by Zn (Scheme 2) only starts in the presence of the carbonyl substrate which is coordinated to the Ti (the "instant method"); both the ketone-> pinacolate and the pinacolate-> alkene steps (Scheme 2) apparently involve a transient reduction of Ti3+ by Zn.This view is supported by experiments in which TiCl2*LiCl is used as a reagent and in which it behaves as a one-electron reductant (Scheme 3).On the basis of these results, the overall stoichiometry of the McMurry reaction utilizing TiCl3(DME)1.5-Zn(Cu) as a reagent can be represented by Eq. (4).High yields (95-97percent) of the alkene 2 in acceptable reaction times can already be achieved with an acetophenone: TiCl3(DME)1.5:Zn(Cu) molar ratio of 1:2:2.A conclusion which can be drawn from the results is that the McMurry reaction when performed with two of the most commonly applied reagents, namely TiCl3-LiAlH4-THF (in fact HTiCl(THF)0.5!) and TiCl3(DME)1.5-Zn(Cu)-DME, is mainly associated with changes in the (formal) oxidation state of titanium between Ti2+ and Ti3+.Keywords: McMurry reaction; TiCl3(1,2-dimethoxyethane); Low valent titanium-ketone complexes

Semiconductor Phostocatalysis. ZnS-Nanocrystallite-Catalyzed Photooxidation of Organic Compounds

Freshly prepared ZnS (nano-ZnS) suspensions catalyze photooxidation of organic substrates under band-gap irradiation with water as a good electron acceptor, while H2 evolves concomitantly.The organic substrates with hetero atoms or carbon-carbon double bonds (?-bonds), such as triethylamine (TEA), diethylamine (DEA), methanol, ethanol, cyclopentene, cyclohexene, 2-methylfuran, toluene, and ethylbenzene, undergo effective one-hole oxidation.This leads to efficient carbon-carbon bond forming reactions between cumulatively formed radicals at the α-carbon adjacent to the hetero atom or the ?-bond.The photooxidation in the presence of a larger quantity of water results in successive oxidation of the intermediary α-carbon radicals, giving the two-hole oxidation products, e.g., DEA and acetaldehyde from TEA and formaldehyde from methanol.The formation of the intermediary α-carbon radical has been clarified by ESR analysis using 2-propanol as an organic substrate.Semi-empirical molecular orbital calculations suggest that the nano-ZnS-catalyzed photooxidation should be predictable from energetics in the formation of the α-carbon radicals through one-hole oxidation and deprotonation, and from change in the bond order of αC-H bond of the α-carbon cation radicals.

Reactivity of the secondary benzylic Grignard reagent from 1-phenylethyl chloride with aldehydes and ketones. More evidence for the rearrangement mechanism in benzyl Grignard reactions

Additional evidence for the mechanism proposed previously to account for diol formation in the reaction of the Grignard reagent from benzyl chloride with aldehydes has been obtained from a study of the interaction of the Grignard reagent from 1-phenylethyl chloride with carbonyl compounds.This Grignard reagent reacts with ketones (except non-enolisable ketones) to give normal alcohols in low yields, and with aldehydes to give diols.However, in contrast to that formed in the reaction of benzylmagnesium chloride, an unstable trienic alcohol formed from the rearrangement of the corresponding alkoxide could be isolated in some case as the major product, providing confirmatory evidence for the existence of an initial reversible rearrangement in the reaction of the benzylic Grignard reagents with carbonyl compounds.

Stereoselectivity in the Condensation Reactions of 1-Phenylethyl Alkyl and Phenyl Ketones with Organometallic Reagents

Stereochemical results of the condensation reactions of a series of ketones, PhCHMeCOR (R= Me, Et, Pri, But, Ph), with various organomagnesium and organolithium derivatives in ethers as solvents are reported.Results are accounted for on the basis of competition between two transition states which may adopt either Karabatsos- or Felkin-type conformations according to the nature of R, the reagent nucleophilicity, and the polarity of solvent.Polar and steric analysis of this reaction allows highly stereoselective syntheses of diastereoisomeric α-phenylalkanols to be devised.