65248-43-3

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• 857824-72-7 2-methyl-3-phenyl-2-propyloxirane 
• 34713-70-7 2-Phenylpropanal 
• 927-77-5 n-propylmagnesium bromide 
• 1823-91-2 1-phenylethyl cyanide 
• 672-65-1 (1-chloroethyl)benzene 
• 141-75-3 butyryl chloride 
• 7664-93-9 sulfuric acid 
• 799781-71-8 2-methyl-1-phenyl-pentane-1,2-diol 
• 492-37-5 hydratropic acid 
• 25145-43-1 2-phenylpropionyl chloride 
• 98-86-2 acetophenone 
• 20247-89-6 cis/trans-2-phenyl-hex-2-ene 
• 1298088-83-1 C₁₂H₁₆O 
• 1942-45-6 4-Octyne 

Relevant academic research and scientific papers

Ketone Synthesis from Benzyldiboronates and Esters: Leveraging α-Boryl Carbanions for Carbon-Carbon Bond Formation

An alkoxide-promoted method for the synthesis of ketones from readily available esters and benzyldiboronates is described. The synthetic method is compatible with a host of sterically differentiated alkyl groups, alkenes, acidic protons α to carbonyl groups, tertiary amides, and aryl rings having common organic functional groups. With esters bearing α-stereocenters, high enantiomeric excess was maintained during ketone formation, establishing minimal competing racemization by deprotonation. Monitoring the reaction between benzyldiboronate and LiOtBu in THF at 23 °C allowed for the identification of products arising from deborylation to form an α-boryl carbanion, deprotonation, and alkoxide addition to form an "-ate" complex. Addition of 4-trifluoromethylbenzoate to this mixture established the α-boryl carbanion as the intermediate responsible for C-C bond formation and ultimately ketone synthesis. Elucidation of the role of this intermediate leveraged additional bond-forming chemistry and enabled the one-pot synthesis of ketones with α-halogen atoms and quaternary centers with four-different carbon substituents.

Photochemical Asymmetric Nickel-Catalyzed Acyl Cross-Coupling

Photochemical enantioselective nickel-catalyzed cross-coupling reactions are difficult to implement. We report a visible-light-mediated strategy that successfully couples symmetrical anhydrides and 4-alkyl dihydropyridines (DHPs) to afford enantioenriched α-substituted ketones under mild conditions. The chemistry does not require exogenous photocatalysts. It is triggered by the direct excitation of DHPs, which act as a radical source and as a reductant, facilitating the turnover of the chiral catalytic nickel complex.

Enantioselective Hydrogen Atom Transfer: Discovery of Catalytic Promiscuity in Flavin-Dependent 'Ene'-Reductases

Flavin has long been known to function as a single electron reductant in biological settings, but this reactivity has rarely been observed with flavoproteins used in organic synthesis. Here we describe the discovery of an enantioselective radical dehalogenation pathway for α-bromoesters using flavin-dependent 'ene'-reductases. Mechanistic experiments support the role of flavin hydroquinone as a single electron reductant, flavin semiquinone as the hydrogen atom source, and the enzyme as the source of chirality.

Regioselective 1,2-Diol Rearrangement by Controlling the Loading of BF3·Et2O and Its Application to the Synthesis of Related Nor-Sesquiterene- and Sesquiterene-Type Marine Natural Products

The regiocontrolled rearrangement of 1,2-diols has been achieved by controlling the loading of BF3·Et2O. Its applicability is showcased by the divergent synthesis of austrodoral, austrodoric acid, and 8-epi-11-nordriman-9-one, as well as a formal synthesis of siphonodictyal B and liphagal. A new light is shed on piancol-type rearrangements that will be useful in diversity-oriented synthesis of related natural products.

Silicon-(thio)urea Lewis acid catalysis

We present a new class of catalysts based on the combination of N,N′-diaryl(thio)ureas and weak silicon Lewis acids (e.g., SiCl 4). Such silicon-(thio)urea catalysts effectively catalyze the stereospecific rearrangement of epoxides to quaternary carbaldehydes.

Nickel/Lewis acid-catalyzed carbocyanation of alkynes using acetonitrile and substituted acetonitriles

Nickel/Lewis acid dual catalysis is found to effect the carbocyanation reaction of alkynes using acetonitrile and substituted acetonitriles to give a range of variously substituted acrylonitriles. The addition of propionitrile across alkynes is also demonstrated briefly to give the corresponding ethylcyanation products in good yields, whereas the reaction of butyronitrile gives significant amounts of hydrocyanation products due possibly to β hydride elimination of a propylnickel intermediate. The reaction of optically active α phenylpropionitrile suggests a reaction mechanism that involves oxidative addition of a CCN bond with retention of its absolute configuration.

Nickel/AlMe2Cl-catalysed carbocyanation of alkynes using arylacetonitriles

Nickel/Lewis acid dual catalysis was found to effect the carbocyanation reaction of alkynes using arylacetonitriles, giving a range of triply substituted acrylonitriles; the reaction of optically active α-phenylpropionitrile suggested a reaction mechanism