35028-06-9

Upstream product

• 875856-04-5 1-o-tolyl-butan-1-one-imine 
• 932-31-0 ortho-tolylmagnesium bromide 
• 141-75-3 butyryl chloride 
• 118-90-1 ortho-methylbenzoic acid 
• 107-92-6 butyric acid 
• 74571-45-2 2-Benzyloxy-pentanenitrile 
• 615-37-2 ortho-methylphenyl iodide 
• 201230-82-2 carbon monoxide 
• 107-08-4 1-iodo-propane 
• 108-88-3 toluene 
• 106-31-0 butanoic acid anhydride 
• 529-19-1 2-Methylbenzonitrile 
• 100-39-0 benzyl bromide 
• 123-73-9 trans-Crotonaldehyde 

Downstream Products

• 799804-25-4 2-mesyloxy-1-(2-methylphenyl)-1-butanone 
• 64897-49-0 1-methoxy-2-[(2-methylphenyl)ethynyl]benzene 
• 195062-59-0 2-methylphenylboronic acid pinacol ester 
• 5407-62-5 hydroxybutyltoluene 
• 83-33-0 inden-1-one 

Relevant academic research and scientific papers

Iridium-Catalyzed Asymmetric Hydrogenation of α-Fluoro Ketones via a Dynamic Kinetic Resolution Strategy

The discrimination of a fluorine atom from a hydrogen atom has been challenging in asymmetric catalysis. We herein report iridium-catalyzed hydrogenation of α-fluoro ketones using a strategy of dynamic kinetic resolution. Both enantiomeric and diastereomeric selectivities were satisfactory in the preparation of β-fluoro alcohols. The DFT calculation revealed a C-F···Na charge-dipole interaction in the transition state of hydride transfer. This noncovalent interaction would be responsible for the diastereomeric control.

Palladium-Catalyzed Carbonylative Coupling of Aryl Iodides with Alkyl Bromides: Efficient Synthesis of Alkyl Aryl Ketones

Alkyl aryl ketones are important structures with applications in many areas of chemistry. Hence, efficient procedures for their production are particularly attractive. In this communication, a general and efficient carbonylative cross-coupling of aryl iodides and unactivated alkyl bromides is presented. By using a simple palladium catalyst, a series of alkyl aryl ketones were synthesized in moderate to excellent yields from readily available alkyl and aryl halides in an In-Ex tube with formic acid as the CO source. In this study both primary and secondary alkyl bromides/iodides were suitable coupling partners. Additionally, this method can also be employed for the late-stage functionalization of complex natural products and polyfunctionalized molecules. (Figure presented.).

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.

Kinetic resolution of aryl alkenylcarbinols catalyzed by Fc-PIP

An effective kinetic resolution of a variety of aryl alkenylcarbinols catalyzed by nonenzymatic acyl transfer catalyst Fc-PIP was developed, affording corresponding unreacted alcohols in good to excellent ee value up to 99% and with selectivity factors up to 24.

Photochemical preparation of highly functionalized 1-indanones

A series of o-alkylphenyl alkyl ketones 1 were synthesized by different methods. The presence of a leaving group X adjacent to the carbonyl group is the special peculiarity of these ketones. Upon irradiation the keto carbonyl group of these compounds undergoes an n-π* excitation followed by a 1,5-hydrogen migration from the o-alkyl substituent to the carbonyl oxygen atom. The thus formed 1,4-diradicals are subject to a very rapid elimination of acid HX, giving 1,5-diradicals. We called this process spin center shift. After intersystem crossing these diradicals cyclize to 1-indanones 20 in good yields. Depending on the solvent and on substituents, o-alkoxyalkyl ketones 22 or benzo-[c]furanes 21 are obtained as byproducts. The mechanism of the cyclization was elucidated by quantum chemical calculations and kinetic measurements.

Friedel-crafts acetylation, propionylation, and butyrylation of toluene catalyzed by solid superacids

The liquid-solid phase acetylation of toluene with acetic anhydride was carried out over solid superacids of sulfated metal oxides (SO4/MeOx) and supported metal oxides (Me1Ox/Me2Oy) selected from the results in the benzoylation of toluene with benzoic anhydride [K. Arata, H. Nakamura, and M. Shouji, Appl. Catal. A: General, 197, 213 (2000)]. The reaction was conducted by adding dropwise a mixture of 2 mmol of acetic anhydride and 2 mL of toluene onto 0.5 g of catalyst suspended in 13 mL of toluene with stirring at 110 °C in the first period of 30 min, followed by stirring the mixture for 2 h. The yields of 2′-, 3′-, and 4′-methylacetophenones in the distribution of 9-10% 2′-, 1-2% 3′and 89-90% 4′-isomers were 24 and 13% for the sulfated metal oxides of SO4/ZrO2 and SO4/SNO2, those by Pt and Ru promoted sulfated zirconias (Pt-, Ru-SO4/ZrO2) being 21 and 28%, respectively. The supported metal oxides of Fe2O3/ ZrO2 and WO3/ZrO2 gave yields of 18 and 15%, respectively. The propionylation and butyrylation of toluene with propionic and butyric anhydrides were performed over SO4/ZrO2, SO4/SnO2, Pt-SO4/ZrO2, and Ru-SO4/ZrO2; the yields of 7-9% o- and 91-93% p-isomers were 31, 26, 32, and 44% for propionylation and 46, 29, 44, and 55% for butyrylation, respectively. The SO4/ZrO2 catalyst gave a 100% yield of 4′-methoxyacetophenone for the acetylation of anisole with acetic anhydride.

A Convenient and Efficient Unsymmetrical Ketone Synthesis from Acid Chlorides and Alkyl Iodides Catalyzed by Palladium

Unsymmetrical ketones are prepared in good or excellent yields by a palladium catalyzed coupling reaction of acid chlorides and alkyl iodides meditated by Zn-Cu couple.

Unsymmetrical Ketone Synthesis via Palladium Catalyzed Carbonylation of Organic Halides

Aryl alkyl (or benzyl) ketones are selectively prepared by the reaction of aryl iodides and alkyl iodides (or benzyl chlorides) in the presence of a stoichiometric amount of zinc-copper couple and a catalytic amount of palladium(O) complex under an atmospheric pressure of carbon monoxide.