61363-11-9

Upstream product

• 3277-89-2 phenethylmagnesium bromide 
• 66408-81-9 4-[(trimethylsilyl)oxy]pentanenitrile 
• 120760-00-1 (1E)-1-Phenyl-1-heptene-3,6-dione 
• 104-53-0 3-phenyl-propionaldehyde 
• 78-94-4 methyl vinyl ketone 
• 102-92-1 cinnamoyl chloride 
• 94806-25-4 (E)-4-(Tri-n-butylstannyl)-3-buten-2-one 
• 89329-61-3 1-(2-methyl-1,3-dioxolan-2-yl)-5-phenylpentan-3-one p-toluenesulfonylhydrazone 
• 100-58-3 phenylmagnesium bromide 
• 220446-49-1 1-phenyl-6-hepten-3-one O-pentafluorobenzoyloxime 
• 75-11-6 diiodomethane 
• 52393-50-7 6-phenyl-2,4-hexanedione 
• 172946-94-0 5-(Benzotriazol-1-yl)-5-ethoxyhept-6-en-2-one 
• 89329-53-3 1-(2-methyl-1,3-dioxolan-2-yl)-2-nitro-5-phenylpentan-3-one 

Downstream Products

• 13380-80-8 2-benzyl-3-methyl-2-cyclopenten-1-one 
• 144284-63-9 4-Methyl-7-(2-phenylethyl)indene 
• 2344-70-9 1-phenyl-3-butanol 
• 2550-26-7 4-Phenyl-2-butanone 

Relevant academic research and scientific papers

Flow synthesis using gaseous ammonia in a Teflon AF-2400 tube-in-tube reactor: Paal-Knorr pyrrole formation and gas concentration measurement by inline flow titration

Using a simple and accessible Teflon AF-2400 based tube-in-tube reactor, a series of pyrroles were synthesised in flow using the Paal-Knorr reaction of 1,4-diketones with gaseous ammonia. An inline flow titration technique allowed measurement of the ammonia concentration and its relationship to residence time and temperature.

Ruthenium-catalyzed three-component coupling via hydrative conjugate addition of alkynes to alkenes: One-pot synthesis of 1,4-dicarbonyl compounds

A catalytic three-way rendezvous: Terminal alkynes undergo metal vinylidene formation, anti-Markovnikov hydration to give a metal acyl complex, and conjugate addition to produce synthetically useful 1,4-dicarbonyl compounds under ruthenium catalysis. This one-pot three-component coupling reaction is a useful platform for further exploration in alkyne functionalization.

Polarity reversal induced by electrochemically generated thiazol-2-ylidenes: The Stetter reaction

The inversion of the normal reactivity (umpolung) of aldehydes has been induced via N-heterocyclic carbenes (NHCs) thiazol-2-ylidenes 2a or 3a, generated by simple electrolyses of solutions containing thiazolium salt 2 or 3. Accordingly, 1,4-dicarbonyl compounds have been obtained, in mild conditions and in moderate to very high yields, via 1,4-addition of the Breslow intermediates to the suitable Michael acceptor. The procedure has been performed in classical organic solvents (VOCs) as well as in room temperature ionic liquids (RTILs). The different reactivity of aliphatic aldehydes vs the one of aromatic and heteroaromatic aldehydes has been emphasized.

2,5-Disubstituted furans from 1,4-alkynediols

1,4-Alkynediols serve as readily available starting materials for isomerisation to 1,4-diketones, which can be converted in situ into the corresponding furans by acid-catalysed dehydration. A range of 2,5-disubstituted furans was prepared using the ruthenium-based catalyst Ru(PPh3)3(CO)H2 with Xantphos at 1 mol % loading.

Zinc-mediated chain extension reaction of 1,3-diketones to 1,4-diketones and diastereoselective synthesis of trans-1,2-disubstituted cyclopropanols

A variety of 1,3-diketones can be efficiently converted into the corresponding 1,4-diketones and trans-1,2-disubstituted cyclopropanols by using organozinc species in one-pot reactions. It was found that 2.3 equiv of CF 3CO2ZnCH2I was effective to give the corresponding chain-extended products in 44-85% yields, while a mixture of organozinc species formed from 4.0 equiv of Et2Zn, 2.0 equiv of CF3CO2H, and 4.0 equiv of CH2I2 resulted in the formation of trans-1,2-disubstituted cyclopropanols with quite good yields and diastereoselectivity.

Synthesis of pyrrole derivatives by palladium-catalyzed cyclization of γ,δ-unsaturated ketone o-pentafluorobenzoyloximes

Various pyrrole derivatives are synthesized from γ,δ-unsaturated ketone O-pentafluorobenzoyloximes by treatment with catalytic amounts of Pd(PPh3)4 and triethylamine via alkylideneaminopalladium(II) intermediates generated by oxidative addition of the oximes to the Pd(0) complex.

Novel Routes to Enol Ethers, Unsymmetrical Ketones, α-Bromoalkyl Ketones, 1,4-Diketones, 2-Ethoxy-2-cyclopenetenones, and α-Keto Enamines

Highly regioselectve SN2' reactions of adducts 6 (readily prepared by reactions of halides with the allyl anion 12 of 11) with Grignard reagents gave enol ethers 13, which were converted (in one-pot reactions from 11) into ketones 14 and α-bromoalkyl ketones 15 in good yields.The monoprotected 1,4-diketone derivative 16 (prepared by Michael addition of the allyl anion 12 with methyl vinyl ketone) was converted both into 1,4-diketones 18 and into protected γ-hydroxyalkyl ketone 20 by propenoyl, or to both functionalities.The allyl anion 12 with α-substituted acetic esters gave α-acylated adducts 24, which underwent in situ unfavored endo-trig cyclization upon treatment with NaH and secondary amines, to give 2-ethoxy-2-cyclopenetenones 27 and 28 and α-keto enamines 25 in good yield.The mechanism for the cyclization is discussed.

Synthesis of 1,4-Diketones by Palladium-Catalyzed Reductive Coupling of Acid Chlorides with (E)-1,2-Bis(tri-n-butylstannyl)ethene or β-Stannyl Enones

The palladium-catalyzed coupling of acid chlorides with (E)-1,2-bis(tri-n-butylstannyl)ethene or β-stannyl enones gives butane-1,4-diones directly by reduction of the intermediate enedicarbonyl derivative by a palladium hydride derived from n-Bu3SnCl.

A NEW ROUTE TO 1,4-DIKETONES AND ITS APPLICATION TO (Z)-JASMONE AND DIHYDROJASMONE SYNTHESIS.

(Z)-Jasmone, dihydrojasmone and other 3-methylcyclopent-2-en-1-ones are easily synthetized starting from aldehydes and 1-(2-methyl-1,3-dioxolane-2-yl)-2-nitroethane as reagent for 3-ketobutyl anion synthon.Nitro-aldol condensation is the chainleghtening reaction followed by oxidation and denitration via p-toluenesulfonylhydrazones of the corresponding α-nitroketones.Removal of protecting groups gives 1,4-diketones which are then cyclized with alkali.

Process for the preparation of ketones

The invention concerns a new process for the preparation of ketones; according to this process ketones are prepared from aldehydes and unsaturated compounds in the presence of bases using quaternary ammonium salts as catalysts.