115665-93-5

Upstream product

• 78-94-4 methyl vinyl ketone 
• 99768-12-4 4-methoxycarbonylphenylboronic acid 
• 100-85-6 N-benzyl-trimethylammonium hydroxide 
• 123-42-2 4-Hydroxy-4-methyl-2-pentanone 
• 1571-08-0 methyl 4-formylbenzoate 
• 1439-36-7 1-triphenylphosphoranylidene-2-propanone 
• 67-64-1 acetone 
• 106-96-7 propargyl bromide 
• 108-22-5 Isopropenyl acetate 

Downstream Products

• 1618091-77-2 (E)-4-(4-(hydroxymethyl)phenyl)but-3-en-2-one 
• 74248-66-1 4-(4-carboxyphenyl)butan-2-one 

Relevant academic research and scientific papers

A selective and benign synthesis of functionalized benzalacetones via Mizoroki-Heck reaction using aryldiazonium salts

Palladium-catalyzed Mizoroki-Heck reactions were carried out in the presence of calcium carbonate in alcoholic solvents. Under these conditions an efficient preparation of functionalized benzalacetones was developed. The reactions were carried out at room temperature and aerobic conditions, giving the products within several minutes in up to 95% isolated yields. Furthermore, some kinetic investigations, mechanistic insights and considerations are presented.

Enantioselective NiH/Pmrox-Catalyzed 1,2-Reduction of α,β-Unsaturated Ketones

The enantioselective 1,2-reduction of α,β-unsaturated ketones was achieved using a NiH catalyst in the presence of pinacolborane. This mild process represents a general method to access a wide variety of structurally diverse α-chiral allylic alcohols in excellent yields and enantioselectivity, as well as very high levels of ambidoselectivity for 1,2- over 1,4-reduction. Furthermore, for reactions on a 10 mmol scale, catalyst loadings as low as 0.5 mol % could be employed to deliver product without any detrimental effect on the yield, enantio-, or ambidoselectivity.

Copper-catalyzed retro-aldol reaction of β-hydroxy ketones or nitriles with aldehydes: Chemo- and stereoselective access to (E)-enones and (E)-acrylonitriles

A copper-catalyzed transfer aldol type reaction of β-hydroxy ketones or nitriles with aldehydes is reported, which enables chemo- and stereoselective access to (E)-α,β-unsaturated ketones and (E)-acrylonitriles. A key step of the in situ copper(i)-promoted retro-aldol reaction of β-hydroxy ketones or nitriles is proposed to generate a reactive Cu(i) enolate or cyanomethyl intermediate, which undergoes ensuing aldol condensation with aldehydes to deliver the products. This reaction uses 1.2 mol% Cu(IPr)Cl (IPr denotes 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) as the catalyst in the presence of 6.0 mol% NaOtBu cocatalyst at room temperature or 70 °C. A range of aryl and heteroaryl aldehydes as well as acrylaldehydes are compatible with many useful functional groups being tolerated. Under the mild and weakly basic conditions, competitive Cannizzaro-type reaction of benzaldehydes and side reactions of base-sensitive functional groups can be effectively suppressed, which show synthetic advantages of this reaction compared to classic aldol reactions. The synthetic potential of this reaction is further demonstrated by the one-step synthesis of biologically active quinolines and 1,8-naphthyridine in excellent yields (up to 91%). Finally, a full catalytic cycle for this reaction has been constructed using DFT computational studies in the context of a retro-aldol/aldol two-stage mechanism. A rather flat reaction energy profile is found indicating that both stages are kinetically facile, which is consistent with the mild reaction conditions.

Morpholinium trifluoroacetate-catalyzed aldol condensation of acetone with both aromatic and aliphatic aldehydes

We report a highly efficient, general and practical method for the aldol condensation of acetone with aromatic and aliphatic aldehydes, using morpholinium trifluoroacetate as a catalyst.

Heck-type coupling vs. conjugate addition in phosphine-rhodium catalyzed reactions of aryl boronic acids with α,β-unsaturated carbonyl compounds: A systematic investigation

The competition between Heck-type coupling and conjugate addition in phosphine-rhodium catalyzed reactions of aryl boronic acids with α,β-unsaturated carbonyls has been systematically investigated in a toluene-H2O biphasic system. Aside from the intrinsic nature of rhodium and the enolization of carbonyls, the phosphine supporting ligand on rhodium, the ratio of aryl boronic acid to α,β-unsaturated carbonyl and the pH value of the aqueous phase were found to affect the competition significantly. Highly selective rhodium-based catalyst systems have therefore been developed for both Heck-type coupling and conjugate addition by synergistically tuning the supporting ligand, the boronic acid to olefin ratio and other reaction conditions. Conjugate addition with selectivity >99% and Heck-type coupling with selectivity of up to 100%, 98% and 84% for acrylates, acrylamides and methyl vinyl ketone, respectively, could be achieved in the rhodium-catalyzed reactions of aryl boronic acids with α,β- unsaturated carbonyls using the corresponding optimized rhodium-based catalyst systems. The Royal Society of Chemistry.

Direct organocatalytic asymmetric heterodomino reactions: The Knoevenagel/Diels-Alder/epimerization sequence for the highly diastereoselective synthesis of symmetrical and nonsymmetrical synthons of benzoannelated centropolyquinanes

Amino acids and amines have been used to catalyze three component hetero-domino Knoevenagel/Diels-Alder/epimerization reactions of readily available various precursor enones (1a-1), aldehydes (2a-p), and 1,3-indandione (3). The reaction provided excellent

Carbonyl propargylation or allenylation by 3-haloprop-1-yne with tin(n) halides and tetrabutylammonium halides

3-Bromoprop-1-yne causes carbonyl propargylation with tin(n) chloride and tetrabutylammonium bromide in water to produce 1-substituted but-3-yn-1-ols, while 3-chloroprop-1-yne causes carbonyl allenylation with tin(II) iodide and tetrabutylammonium iodide in 1,3-dimethylimidazolidin-2-one to produce 1-substituted buta-2,3-dien-1-ols.

Nickel- and Palladium-Catalyzed Aldol-Type Condensation by Enol Esters

PdCl2(PhCN)2-SnCl2, bis(1,5-cyclooctadiene)nickel(0) /PPh3-Zn, NiBr2(PPh3)2-Zn, or Pd-(OAc)2/PPh3-Zn catalytic systems induced aldol-type condensation of isopropenyl acetate with aldehydes to produce 4-substituted (E)-3-buten-2-ones.PdCl2(PhCN)2-SnCl2 was utilized in the aldol-type reaction with any arenecarbaldehyde, bearing either an electron-donating group or an electron-withdrawing group, at 50 deg C in acetonitrile.Catalytic systems using zinc, in particular Ni(cod)2/PPh3-Zn, exhibited some high chemoselectivities at 60 deg C in dioxane: (1) an aldehyde only reacted in the presence of an internal ester or ketone, (2) olefinic aldehydes only reacted in the presence of saturated aliphatic aldehydes, (3) reactivity in the condensation with substituted benzaldehydes is the inverse of that in usual nucleophilic addition to carbonyl compound, and (4) 2-methoxybenzaldehyde only reacted in the presence of 4-methoxybenzaldehyde.Using PdCl2(PhCN)2-SnCl2, Ni(cod)2/PPh3-Zn, or Pd(OAc)2/PPh3-Zn, cyclic enol ester, namely 5-methyl-2(3H)-furanone also caused aldol-type reaction with carbonyl compounds.The reaction with Ni(cod)2/PPh3-Zn or Pd(OAc)2/PPh3-Zn at 60 deg C in dioxane selectively produced 5-substituted 4-acetyl-2(5H)-furanones via dehydrogenation of γ-substituted β-acetyl-γ-butyrolactones.

Palladium-catalyzed aldol-type condensation by enol esters with SnCl2

Using PdCl2(PhCN)2-SnCl2, enol esters caused aldol-type condensation with aldehydes at 50°C in acetonitrile to produce (E)-α,β-unsaturated carbonyl compounds. Cyclic enol ester such as α-angelicalactone also reacted with aldehydes under the same conditions to afford γ-substituted β-acetyle-γ-butyrolactones and/or 5-substituted 4-acetyl-2(5H)-furanones.

Process for producing p-n-alkylbenzoic acid

p-n-Alkylbenzoic acids having high purity without containing isomers are important as intermediates for liquid crystals. The p-n-alkylbenzoic acid is produced by reacting a p-formylbenzoic acid or its ester with a ketone having the formula STR1 wherein R represents a C1 -C18 n-alkyl or n-alkenyl group in the presence of a basic catalyst to obtain an unsaturated ketone compound having the formula STR2 wherein R is defined above and X represents hydrogen atom or a C1 -C6 alkyl group, and then, hydrogenating and reducing the unsaturated ketone compound to obtain the p-n-alkylbenzoic acid having the formula STR3