108897-09-2

Upstream product

• 64-17-5 ethanol 
• 4773-35-7 1-chloro-1-phenylpropan-2-one 
• 582-25-2 Potassium benzoate 
• 98-88-4 benzoyl chloride 
• 23022-83-5 1-bromo-1-phenyl-2-propanone 
• 4187-87-5 1-Phenyl-2-propyn-1-ol 
• 65-85-0 benzoic acid 
• 37559-19-6 3-(phenyl)prop-2-yn-1-yl benzoate 
• 614-45-9 tert-Butyl peroxybenzoate 
• 103-79-7 1-phenyl-acetone 
• 3893-35-4 1-diazo-1-phenyl-2-propanone 

Relevant academic research and scientific papers

Asymmetric Catalytic Insertion of α-Diazo Carbonyl Compounds into O-H Bonds of Carboxylic Acids

An efficient enantioselective insertion of α-diazoesters and α-diazoketones into O-H bonds of carboxylic acids was realized by the use of Rh2(OAc)4 and a chiral guanidine. Optically active α-acyloxy carbonyl compounds were generated under mild reaction conditions in high yields (up to 99%) and good enantioselectivities (up to 97.5:2.5 er).

Synthesis of α-acyloxyketone derivatives via the platinum-catalyzed migration of propargylic esters

The synthesis of α-acyloxyketones via the migration of a propargylic ester followed by the intramolecular nucleophilic addition of the resulting allene was achieved using a cationic platinum catalyst. The optimized conditions for this transformation were

Ruthenium Carboxylate Complexes as Efficient Catalysts for the Addition of Carboxylic Acids to Propargylic Alcohols

Ruthenium complexes [Ru(CO)2(PPh3)2(O2CR)2] - 3a (R = CH2OCH3), 3b (R = iPr), 3c (R = tBu), 3d (R = 2-cC4H3O), and 3e (R = Ph) - were synthesized

Atom Economic Ruthenium-Catalyzed Synthesis of Bulky β-Oxo Esters

Ruthenium complexes with the formulae Ru(CO)2(PR3)2(O2CPh)2 [6a-h; R=n-Bu, p-MeO-C6H4, p-Me-C6H4, Ph, p-Cl-C6H4, m-Cl-C6H4, p-CF3-C6H4, m,m′-(CF3)2C6H3] were prepared by treatment of triruthenium dodecacarbonyl [Ru3(CO)12] with the respective phosphine and benzoic acid or by the conversion of Ru(CO)3(PR3)2 (8e-h) with benzoic acid. During the preparation of 8, ruthenium hydride complexes of type Ru(CO)(PR3)3(H)2 (9g, h) could be isolated as side products. The molecular structures of the newly synthesized complexes in the solid state are discussed. Compounds 6a-h were found to be highly effective catalysts in the addition of carboxylic acids to propargylic alcohols to give valuable β-oxo esters. The catalyst screening revealed a considerably influence of the phosphine′s electronic nature on the resulting activities. The best performances were obtained with complexes 6g and 6h, featuring electron-withdrawing phosphine ligands. Additionally, catalyst 6g is very active in the conversion of sterically demanding substrates, leading to a broad substrate scope. The catalytic preparation of simple as well as challenging substrates succeeds with catalyst 6g in yields that often exceed those of established literature systems. Furthermore, the reactions can be carried out with catalyst loadings down to 0.1mol% and reaction temperatures down to 50 C.

Copper-catalyzed benzylic oxidation of C(sp3)-H bonds

A selective oxidation of benzylic C(sp3)-H bonds to C(sp 3)-O bonds catalyzed by copper complexes of quinoline-imine ligands was developed with peresters as oxidants under mild reaction conditions, which converted benzylic methylenes directly into benzylic alcohols and esters by means of direct C-H bond functionalization.

Ruthenium carboxylate complexes as easily prepared and efficient catalysts for the synthesis of β-oxopropyl esters

The easily prepared complex cis-[Ru(κ2-O 2CMe)2(PPh3)2] is an effective catalyst for the addition of carboxylic acids to propargyl alcohols to afford β-oxopropyl esters. The reaction is tolerant to a

Ruthenium(IV)-catalyzed markovnikov addition of carboxylic acids to terminal alkynes in aqueous medium

The dimeric bis(allyl)ruthenium(IV) complex [{RuCl(μ-Cl)( η3:η3-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) (5) and several mononuclear species trans-[RuCl2(η3: η3-C10H16)(L)] (L = two-electron-donor ligand) (6) derived from 5 have been checked as catalysts for the addition of carboxylic acids onto terminal alkynes using water as a green reaction medium. The best results in terms of activity and regioselectivity were obtained with the mononuclear derivative trans-[RuCl2(η3: η3-C10H16)(PPh3)] (6a), which was able to promote the selective Markovnikov addition of both aromatic and aliphatic carboxylic acids to a large variety of terminal alkynes, enynes, and diynes as well as propargylic alcohols. In this way, a wide number of enol esters and β-oxo esters could be synthesized in moderate to good yields under mild conditions (60 °C) in an aqueous medium.

Ruthenium-catalyzed synthesis of β-oxo esters in aqueous medium: Scope and limitations

The ability of the hydrosoluble ruthenium(ii) complexes [RuCl 2(η6-arene)(PTA)] 3a-d, [RuCl2(η 6-arene)(PTA-Bn)] 4a-d, [RuCl2(η6-arene) (DAPTA)] 5a-d, [RuCl2(η6-arene)(TPPMS)] 6a-d (arene = C6H6, p-cymene, 1,3,5-C6H3Me 3, C6Me6) to promote the atom-economic formation of β-oxo esters, by addition of carboxylic acids to terminal propargylic alcohols in water has been explored. Scope, limitations and catalyst recycling have been evaluated using the most active catalyst [RuCl 2(η6-C6H6)(TPPMS)], 6a.

Conversion of propargylic alcohols to β-oxo esters catalyzed by novel ruthenium-phosphoramidite complexes

A series of half-sandwich phosphoramidite complexes of ruthenium were synthesized and employed as catalysts in the atom-economical formation of β-oxo esters from carboxylic acids and propargylic alcohols. Reaction of the phosphoramidites (R)-BINOL-PNR2 (R=Me, 1a; i-Pr, 1b; benzyl, 1c) and (rac)-6,6′-dibromo-BINOL-PNMe2 (1d) with the dimeric p-cymene-ruthenium dichloride complex, [RuCl2(p-cymene)]2, gave the complexes [RuCl2(p-cymene)(L)] (L=1a, 7a; 1b, 7b; 1c, 7c; 1d, 7d) in 96-66% yield. Accordingly, reaction of (R)-BINOL(8H)-PNMe2 (2a) and (R)-BINOL(8H)-PN-(benzyl)2 (2b) with [RuCl2(p-cymene)] 2 afforded the complexes [RuCl2(p-cymene)(L)] (L=2a, 8a; 2b, 8b) in 82% and 86% yield. In a similar reaction, treatment of (R)-BIPHEN-PNMe2 (9) with [RuCl2(p-cymene)] 2 gave the complex [RuCl2(p-cymene)(9)] (11) in 60% yield. Finally, phosphoramidite 1b reacted with [RuCl2(C6Me 6)]2 to give [RuCl2(C6Me 6)(1b)] (12) in 78% yield. All novel complexes are catalytically active in the formation of β-oxo esters from propargylic alcohols and carboxylic acids. Standard conditions involve cyclohexane solvent, propargylic alcohol (1.0 equiv.), carboxylic acid (1.0 equiv.), ruthenium catalyst (1.5 mol%), and 90°C for 5-18 h. Isolated yields of the β-oxo esters range from 87 to 16% and show broad substrate generality. The reaction proceeds without racemization if a chiral propargylic alcohol is employed. The method is practical as no additives are required and the exclusion of oxygen and moisture is not needed. Complex 7c turned out to be the most effective catalyst (5 h reaction time), showing that the ligand structure has a profound impact on the catalytic performance. The crystal structure of 7a was determined, confirming an octahedral coordination geometry about the ruthenium center.