43008-78-2

Upstream product

• 99-90-1 para-bromoacetophenone 
• 100-51-6 benzyl alcohol 
• 98-80-6 phenylboronic acid 
• 3562-73-0 1-(4-phenyl-phenyl)-1-ethanol 
• 100-42-5 styrene 
• 92-92-2 biphenyl-4-carboxylic acid 
• 14371-10-9 (E)-3-phenylpropenal 
• 5122-94-1 4-biphenylboronic acid 
• 478282-10-9 1-biphenyl-4-yl-3-phenyl-prop-2-yn-1-ol 
• 122-97-4 3-Phenyl-1-propanol 
• 17763-78-9 4-phenylphenyl triflate 
• 3597-91-9 biphenyl-4-yl methanol 
• 536-74-3 phenylacetylene 
• 92-91-1 biphenyl-4-acetaldehyde 

Downstream Products

• 113478-83-4 2-Benzyl-3-biphenyl-4-yl-1,2-dihydro-quinoxaline 
• 113497-74-8 1-Biphenyl-4-yl-2-bromo-3-phenyl-propan-1-one 

Relevant academic research and scientific papers

Selective catalytic synthesis of α-alkylated ketones and β-disubstituted ketones via acceptorless dehydrogenative cross-coupling of alcohols

Herein, a phosphine-free pincer ruthenium(III) catalyzed β-alkylation of secondary alcohols with primary alcohols to α-alkylated ketones and two different secondary alcohols to β-branched ketones are reported. Notably, this transformation is environmentally benign and atom efficient with H2O and H2 gas as the only byproducts. The protocol is extended to gram-scale reaction and for functionalization of complex vitamin E and cholesterol derivatives.

Direct conversion of secondary propargyl alcohols into 1,3-di-arylpropanoneviaDBU promoted redox isomerization and palladium assisted chemoselective hydrogenation in a single pot operation

Palladium(ii)acetate is found to be an efficient catalyst for the single-step conversion of secondary propargyl alcohols to 1,3-diarylpropanone derivatives under mild basic conditions. The reaction is believed to proceedviaredox isomerisation of secondary propargyl alcohols followed by chemoselective reduction of an enone double bond with formic acid as an adequate hydrogen donor. A large number of 1,3-diarylpropanone derivatives may readily be prepared from a milligram to a multigram scale.

Ligand-controlled phosphine-free Co(II)-catalysed cross-coupling of secondary and primary alcohols

Cobalt(II) complexes (5 mol% Co) bearing phosphine-free N?N?N pincer ligands efficiently catalyze C–C coupling of secondary and primary alcohols to selectively form α-alkylated ketones with a good functional group compatibility using NaOH (20 mol%) as a base at 120 °C. The NH group on the N?N?N–Co(II) precatalyst controls the activity and selectivity. This simple catalytic system is involved in the synthesis of quinolones via the dehydrogenative annulation of 2-aminobenzyl alcohols with secondary alcohols.

Ketone Synthesis by a Nickel-Catalyzed Dehydrogenative Cross-Coupling of Primary Alcohols

An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon-carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.

Ketone Synthesis by a Nickel-Catalyzed Dehydrogenative Cross-Coupling of Primary Alcohols

An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon-carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.

C?C Bond Formation of Benzyl Alcohols and Alkynes Using a Catalytic Amount of KOtBu: Unusual Regioselectivity through a Radical Mechanism

We report a C?C bond-forming reaction between benzyl alcohols and alkynes in the presence of a catalytic amount of KOtBu to form α-alkylated ketones in which the C=O group is located on the side derived from the alcohol. The reaction proceeds under thermal conditions (125 °C) and produces no waste, making the reaction highly atom efficient, environmentally benign, and sustainable. Based on our mechanistic investigations, we propose that the reaction proceeds through radical pathways.

Transition-Metal-Free Highly Chemoselective and Stereoselective Reduction with Se/DMF/H2O System

A novel metal-free reduction system, in which H2Se (or HSe-) produced in situ from Se/DMF/H2O acts as the active reducing species, has been developed. By using water as an inexpensive, safe, and environmentally friendly surrogate as the hydrogen donor, this new reduction system incorporating Se/DMF/H2O displayed high selectivity and good activity in the reduction of α,β-unsaturated ketones and alkynes. Therefore, this reduction system has great potential to be a general and practical reduction methodology in organic transformation.

Dirhodium(ii)/P(t-Bu)3 catalyzed tandem reaction of α,β-unsaturated aldehydes with arylboronic acids

Phosphine ligated dirhodium(ii) acetate is advocated as a catalyst for the synthesis of aryl alkyl ketones by the tandem reaction of α,β-unsaturated aromatic or aliphatic aldehydes with arylboronic acids. This tandem procedure included arylation followed by the isomerization reaction. This method exhibits good functional group tolerance and has a broad substrate scope. With the conjugated aldehydes, the one-step synthesis of γ,δ-unsaturated ketones was realized through this reaction. It is noteworthy that the length of the Rh-P bond is an important factor affecting catalytic reactions. The comparative analysis of the crystal structures of axially alkylphosphane and arylphosphane ligated dirhodium(ii) acetate revealed that the shorter Rh-P bond length favors the isomerization process as compared to the longer one. In addition, the dirhodium(ii) compound can be recovered after the completion of the reaction.

Iridium(III)- benzoxazolyl and benzothiazolyl phosphine ligands catalyzed versatile alkylation reactions with alcohols and the synthesis of quinolines and indole

A series of benzoxazolyl and benzothiazolyl phosphine ligands 4a-4g were synthesized and characterized, which prepared from commercially available 2-aminophenol/2-aminobenzenethiol and 2-bromobenzaldehyde via cyclization and phosphination. The representative ligands 4c and 4e were determined by single-crystal X-ray diffraction. The corresponding iridium complexes could be generated in situ when [Cp*IrCl2]2 (Cp* = pentamethylcyclopentadienyl) encountered ligands. The molecular structures of complexes 5c and 5e were crystallographically characterized. The dihedral angles of N (1)-C (1)-C (8)-C (9) showed an increasing twist compared with the corresponding ligand. The iridium (III) catalysts were screened, [Cp*IrCl2]2/4a proved to be the optimal catalyst, which exhibited efficient catalytic activity toward versatile alkylations including ketones, secondary alcohols and amines with primary alcohols. Additionally, the synthesis of quinolines from ketones with 2-aminobenzyl alcohol by intermolecular cyclization and indole from 2-(2-aminophenyl)ethanol by intramolecular cyclization were achieved under the optimized conditions.

In Water and under Mild Conditions: α-Alkylation of Ketones with Alcohols by Phase-Transfer-Assisted Borrowing Hydrogen Catalysis

Borrowing hydrogen is a powerful and green technique that allows readily available alcohols to be used as alkylating agents and produces water as the only by-product. Nevertheless, harsh conditions such as high temperatures and organic solvents are usually required. Herein, we present a strategy to perform the α-alkylation of ketones in aqueous media at mild temperatures by combining borrowing hydrogen with phase-transfer catalysis. A broad scope of methyl ketones was functionalized with alkyl and benzyl alcohols in moderate to good yields at 40 °C. The protocol was also highly effective at large scale and room temperature.