28861-24-7

Upstream product

• 39098-75-4 3-cyclohexylpropionyl chloride 
• 768-03-6 Phenyl vinyl ketone 
• 110-83-8 cyclohexene 
• 695-12-5 vinylcyclohexane 
• 100-51-6 benzyl alcohol 
• 100-59-4 phenylmagnesium chloride 
• 1750-36-3 (E)-N-benzylidenebenzenamine 
• 122-57-6 1-Phenylbut-1-en-3-one 
• 122248-91-3 3-cyclohexyl-1-phenyl-propenone 
• 98-86-2 acetophenone 
• 100-49-2 cyclohexylmethyl alcohol 
• 4249-72-3 2-phenoxy-1-phenylethanol 
• 98-85-1 1-Phenylethanol 
• 823-76-7 Cyclohexyl methyl ketone 

Downstream Products

• 905590-34-3 2-amino-5-(cyclohexylmethyl)-4-phenylthiophene-3-carboxylic acid ethyl ester 

Relevant academic research and scientific papers

A Proton-Responsive Pyridyl(benzamide)-Functionalized NHC Ligand on Ir Complex for Alkylation of Ketones and Secondary Alcohols

A Cp*Ir(III) complex (1) of a newly designed ligand L1 featuring a proton-responsive pyridyl(benzamide) appended on N-heterocyclic carbene (NHC) has been synthesized. The molecular structure of 1 reveals a dearomatized form of the ligand. The protonation of 1 with HBF4 in tetrahydrofuran gives the corresponding aromatized complex [Cp*Ir(L1H)Cl]BF4 (2). Both compounds are characterized spectroscopically and by X-ray crystallography. The protonation of 1 with acid is examined by 1H NMR and UV-vis spectra. The proton-responsive character of 1 is exploited for catalyzing α-alkylation of ketones and β-alkylation of secondary alcohols using primary alcohols as alkylating agents through hydrogen-borrowing methodology. Compound 1 is an effective catalyst for these reactions and exhibits a superior activity in comparison to a structurally similar iridium complex [Cp*Ir(L2)Cl]PF6 (3) lacking a proton-responsive pendant amide moiety. The catalytic alkylation is characterized by a wide substrate scope, low catalyst and base loadings, and a short reaction time. The catalytic efficacy of 1 is also demonstrated for the syntheses of quinoline and lactone derivatives via acceptorless dehydrogenation, and selective alkylation of two steroids, pregnenolone and testosterone. Detailed mechanistic investigations and DFT calculations substantiate the role of the proton-responsive ligand in the hydrogen-borrowing process.

Cyclometalated Ruthenium Pincer Complexes as Catalysts for the α-Alkylation of Ketones with Alcohols

Ruthenium PNP pincer complexes bearing supplementary cyclometalated C,N-bound ligands have been prepared and fully characterized for the first time. By replacing CO and H? as ancillary ligands in such complexes, additional electronic and steric modifications of this topical class of catalysts are possible. The advantages of the new catalysts are demonstrated in the general α-alkylation of ketones with alcohols following a hydrogen autotransfer protocol. Herein, various aliphatic and benzylic alcohols were applied as green alkylating agents for ketones bearing aromatic, heteroaromatic or aliphatic substituents as well as cyclic ones. Mechanistic investigations revealed that during catalysis, Ru carboxylate complexes are predominantly formed whereas neither the PNP nor the CN ligand are released from the catalyst in significant amounts.

Method for synthesizing alpha-alkylated ketone in water

The invention discloses a method for synthesizing alpha-alkylated ketone in water. The method comprises the following steps: adding ketone, compound alcohol, a transition metal iridium catalyst, an alkali and a solvent, namely water into a reaction container, carrying out a reflux reaction on a reaction mixture in the air for several hours, carrying out cooling to room temperature, carrying out rotary evaporation to remove the solvent, and carrying out column separation (ethyl acetate/petroleum ether) to obtain a target compound, namely alpha-alkylated ketone. A reaction equivalent substrate is used in the reaction process, so raw material waste is avoided; equivalent alkali is used, so better environmental protection performance is obtained; water reflux reaction conditions are milder; and non-toxic and harmless pure water is used as the solvent in the reaction, only water is generated as a by-product, so atom reaction economy is high, and the requirements of green chemistry are met.

Iron-Catalyzed, Iminyl Radical-Triggered Cascade 1,5-Hydrogen Atom Transfer/(5+2) or (5+1) Annulation: Oxime as a Five-Atom Assembling Unit

By integration of iminyl radical-triggered 1,5-hydrogen atom transfer and (5+2) or (5+1) annulation processes, a series of structurally novel and interesting azepine and spiro-tetrahydropyridine derivatives have been successfully prepared in moderate to good yields. This method utilizes FeCl2 as the catalyst and readily available oximes as five-atom units, while showcasing broad substrate scope and good functional group compatibility. The annulation products can be easily converted into many valuable compounds. Moreover, DFT calculation studies are performed to provide some insights into the possible reaction mechanisms for the (5+2) and (5+1) annulations.

Sustainable and Selective Alkylation of Deactivated Secondary Alcohols to Ketones by Non-bifunctional Pincer N-heterocyclic Carbene Manganese

A sustainable and green route to access diverse functionalized ketones via dehydrogenative–dehydrative cross-coupling of primary and secondary alcohols is demonstrated. This borrowing hydrogen approach employing a pincer N-heterocyclic carbene Mn complex displays high activity and selectivity. A variety of primary and secondary alcohols are well tolerant and result in satisfactory isolated yields. Mechanistic studies suggest that this reaction proceeds via a direct outer-sphere mechanism and the dehydrogenation of the secondary alcohol substrates plays a vital role in the rate-limiting step.

Mn-Enabled Radical-Based Alkyl-Alkyl Cross-Coupling Reaction from 4-Alkyl-1,4-dihydropyridines

Highly efficient alkylation of β-chloro ketones and their derivatives was achieved by means of domino dehydrochlorination/Mn-enabled radical-based alkyl-alkyl cross-coupling reaction. In situ-generated α,β-unsaturated ketones and their analogues were identified as the reaction intermediates. Known bioactive compounds, such as melperone and azaperone, could be easily prepared from β-chloropropiophenone in two steps.

Regioselective Vinylation of Remote Unactivated C(sp3)?H Bonds: Access to Complex Fluoroalkylated Alkenes

Regioselective incorporation of a particular functional group into aliphatic sites by direct activation of unreactive C?H bonds is of great synthetic value. Despite advances in radical-mediated functionalization of C(sp3)?H bonds by a hydrogen-atom transfer process, the site-selective vinylation of remote C(sp3)?H bonds still remains underexplored. Reported herein is a new protocol for the regioselective vinylation of unactivated C(sp3)?H bonds. The remote C(sp3)?H activation is promoted by a C-centered radical instead of the commonly used N and O radicals. The reaction possesses high product diversity and synthetic efficiency, furnishing a plethora of synthetically valuable E alkenes bearing tri-/di-/mono-fluoromethyl and perfluoroalkyl groups.

The α-alkylation of ketones with alcohols in pure water catalyzed by a water-soluble Cp?Ir complex bearing a functional ligand

A water-soluble dinuclear Cp?Ir complex bearing 4,4′,6,6′-tetrahydroxy-2,2′-bipyrimidine as a bridging ligand was found to be a highly effective catalyst for the α-alkylation of ketones with alcohols in pure water. In the presence of catalyst (0.5 mol%), a series of desirable products were obtained with high reaction economy under environmentally benign conditions. The importance of the hydroxy group in the ligand for catalytic hydrogen transfer was confirmed by mechanism experiments. Furthermore, the application of this catalytic system for the synthesis of a biologically active molecule donepezil in pure water has been accomplished. Notably, this research would facilitate the progress of C-C bond-forming reactions in water catalyzed by water-soluble metal-ligand bifunctional catalysts.

Controlling the selectivity and efficiency of the hydrogen borrowing reaction by switching between rhodium and iridium catalysts

The catalytic alkylation of ketones with alcohols via the hydrogen borrowing methodology (HB) has the potential to be a highly efficient approach for forming new carbon-carbon bonds. However, this transformation can result in more than one product being formed. The work reported here utilises bidentate triazole-carbene ligated iridium and rhodium complexes as catalysts for the selective formation of alkylated ketone or alcohol products. Switching from an iridium centre to a rhodium centre in the complex resulted in significant changes in product selectivity. Other factors-base, base loading, solvent and reaction temperature-were also investigated to tune the selectivity further. The optimised conditions were used to demonstrate the scope of the reaction across 17 ketones and 14 alcohols containing a variety of functional groups. A series of mechanistic investigations were performed to probe the reasons behind the product selectivity, including kinetic and deuterium studies.

Ruthenium-Catalyzed β-Alkylation of Secondary Alcohols and α-Alkylation of Ketones via Borrowing Hydrogen: Dramatic Influence of the Pendant N-Heterocycle

Three bidentate ruthenium(II) complexes with a pyridonate fragment were prepared and fully characterized. These complexes are structurally similar, but differ in their pendant substituents. Complex 1 contains a phenyl unit, whereas complexes 2 and 3 have uncoordinated thienyl and thiazolyl groups, respectively. These complexes were tested as catalysts for β-alkylation of secondary alcohols with primary alcohols, and 3 shows the highest activity, suggesting the thiazolyl ring participates in the catalytic process. Furthermore, 3 is an excellent catalyst for α-alkylation of ketones with primary alcohols. Various α-alkylated ketones were synthesized in high yields, by using 0.05 mol % 3 and 0.25 equiv of t-BuOK within 30 min.