146790-89-8

Upstream product

• 24425-75-0 1-(1-chloropropyl)-4-methylbenzene 
• 592-04-1 mercury(II) cyanide 
• 495-40-9 propiophenone 
• 146767-34-2 4-Methylphenylazo tert-butyl sulfide 
• 855243-84-4 1-phenyl-2-p-tolyl-butane-1,2-diol 
• 77134-00-0 (E)-4-methylcinnamyl acetate 
• 1204518-02-4 4-methylphenyl(2,4,6-trimethylphenyl)iodonium triflate 
• 120869-79-6 (Z)-trimethyl((1-phenylbut-1-en-1-yl)oxy)silane 
• 99-99-0 1-methyl-4-nitrobenzene 
• 4294-57-9 para-methylphenylmagnesium bromide 

Relevant academic research and scientific papers

Rh-Catalyzed Coupling of Aldehydes with Allylboronates Enables Facile Access to Ketones

We present herein a novel strategy for the preparation of ketones from aldehydes and allylic boronic esters. This reaction involves the allylation of aldehydes with allylic boronic esters and the Rh-catalyzed chain-walking of homoallylic alcohols. The key to this successful development is the protodeboronation of alkenyl borylether intermediate via a tetravalent borate anion species in the presence of KHF2 and MeOH. This approach features mild reaction conditions, broad substrate scope, and excellent functional group tolerance. Mechanistic studies also supported that the tandem allylation and chain-walking process were involved.

Enantioselective α-Arylation of Ketones via a Novel Cu(I)-Bis(phosphine) Dioxide Catalytic System

A novel catalytic system based on copper(I) and chiral bis(phosphine) dioxides is described. This allows the arylation of silyl enol ethers to access enolizable α-arylated ketones in good yields and enantiomeric excess up to 95%. Noncyclic ketones are amenable substrates with this method, which complements other approaches based on palladium catalysis. Optimization of the ligand structure is accomplished via rational design driven by correlation analysis. Preliminary mechanistic hypotheses are also evaluated in order to identify the role of chiral bis(phosphine) dioxides.

Palladium-catalyzed denitrative α-arylation of ketones with nitroarenes

The palladium-catalyzed α-arylation of ketones with readily available nitroarenes and nitroheteroarenes provides access to useful α-aryl and α-heteroaryl ketones. The use of the Pd/ BrettPhos catalysts was critical to achieve high efficiency for these transformations, whereas other catalysts led to decreased yields or no conversions. The intramolecular type substrate was also applied in this methodology and gave a chromone derivative. Polyaromatic carbonyl compounds can be easily obtained by multicomponent tandem reactions, via nucleophilic aromatic substitution (SNAr) or cross-coupling reaction followed by this denitrative arylation. Kinetic experiments show that the electronic effect of nitrobenzenes has a greater effect on the reaction rate than the electronic effect of ketones.

Nickel catalyzed α-arylation of ketones with aryltrimethylammonium triflates

Nickel-catalyzed α-arylation of ketones involving aromatic C-N cleavage has been accomplished. Intermolecular coupling of aromatic ketones with a variety of aryltrimethylammonium triflates was achieved in the presence of Ni(COD)2, IPr·HCl, and LiOBut, giving α-arylated ketones in reasonable to excellent yields.

α-arylation vs. α-arylhydrazonylation of alkyl aryl ketones with arylazo tert-butyl sulfides

Potassium enolates of alkyl aryl ketones react selectively in DMSO with phenylazo 1a and 4-methylphenylazo tert-butyl sulfide 1b undergoing respectively effective α-phenylation via S(RN)1 and α-(4-methylphenyl)hydrazonylation via elimination-addition.