10496-72-7

Upstream product

• 1669-49-4 3-(4-methoxyphenyl)-1-phenylpropan-1-one 
• 959-33-1 3-(4-methoxyphenyl)-1-phenylprop-2-en-1-one 
• 22252-15-9 trans-4-methoxychalcone 
• 109643-11-0 1-phenyl-3-(4-methoxyphenyl)prop-2-yn-1-ol 
• 98-85-1 1-Phenylethanol 
• 105-13-5 4-Methoxybenzyl alcohol 
• 123-11-5 4-methoxy-benzaldehyde 
• 98-86-2 acetophenone 

Downstream Products

• 20442-73-3 (1E)-3-(4-methoxyphenyl)-1-phenylpropene 
• 53400-03-6 1-Methoxy-3-(p-methoxyphenyl)-1-phenylpropan 
• 93010-66-3 4-(2,3-dibromo-3-phenyl-propyl)-anisole 
• 35856-80-5 4-(3-phenylallyl)anisole 

Relevant academic research and scientific papers

Carbon-carbon bond formation between secondary alcohols and aldehydes under ruthenium-catalyzed redox shuttle

Secondary alcohols are coupled with aldehydes in dioxane in the presence of a catalytic amount of a ruthenium catalyst along with KOH to give coupled ketones or coupled secondary alcohols depending on the molar ratio of secondary alcohols to aldehydes and the presence (or absence) of a sacrificial hydrogen acceptor. Copyright

Phosphine-free pincer-ruthenium catalyzed biofuel production: High rates, yields and turnovers of solventless alcohol alkylation

Phosphine-free pincer-ruthenium carbonyl complexes based on bis(imino)pyridine and 2,6-bis(benzimidazole-2-yl) pyridine ligands have been synthesized. For the β-alkylation of 1-phenyl ethanol with benzyl alcohol at 140 °C under solvent-free conditions, (Cy2NNN)RuCl2(CO) (0.00025 mol%) in combination with NaOH (2.5 mol%) was highly efficient (ca. 93% yield, 372?000 TON at 12?000 TO h-1). These are the highest reported values hitherto for a ruthenium based catalyst. The β-alkylation of various alcohol combinations was accomplished with ease which culminated to give 380?000 TON at 19?000 TO h-1 for the β-alkylation of 1-phenyl ethanol with 3-methoxy benzyl alcohol. DFT studies were complementary to mechanistic studies and indicate the β-hydride elimination step involving the extrusion of acetophenone to be the overall RDS. While the hydrogenation step is favored for the formation of α-alkylated ketone, the alcoholysis step is preferred for the formation of β-alkylated alcohol. The studies were extended for the upgradation of ethanol to biofuels. Among the pincer-ruthenium complexes based on bis(imino)pyridine, (Cy2NNN)RuCl2(CO) provided high productivity (335 TON at 170 TO h-1). Sterically more open pincer-ruthenium complexes such as (Bim2NNN)RuCl2(CO) based on the 2,6-bis(benzimidazole-2-yl) pyridine ligand demonstrated better reactivity and gave not only good ethanol conversion (ca. 58%) but also high turnovers (ca. 2100) with a good rate (ca. 710 TO h-1). Kinetic studies indicate first order dependence on concentration of both the catalyst and ethanol. Phosphine-free catalytic systems operating with unprecedented activity at a very low base loading to couple lower alcohols to higher alcohols of fuel and pharmaceutical importance are the salient features of this report. This journal is

Ruthenium(III)-Catalyzed β-Alkylation of Secondary Alcohols with Primary Alcohols

A Ru(III)-NNN complex bearing a pyridyl-supported pyrazolyl-imidazolyl ligand was synthesized and utilized as the catalyst for the direct β-alkylation of secondary alcohols with primary alcohols. β-Alkylated secondary alcohols were obtained in moderate to high yields with water formed as the byproduct through a hydrogen borrowing pathway. The present protocol provides a concise atom-economical and environmentally benign method for C-C bond formation.

Iron-Catalyzed α-Alkylation of Ketones with Alcohols

A general and benign iron-catalyzed α-alkylation reaction of ketones with primary alcohols has been developed. The key to success of the reaction is the use of a Kn?lker-type complex as catalyst (2 mol %) in the presence of Cs2CO3 as base (10 mol %) under hydrogen-borrowing conditions. Using 2-aminobenzyl alcohol as alkylation reagent allows for the "green" synthesis of quinoline derivatives.

Direct β-alkylation of secondary alcohols with primary alcohols catalyzed by a Cp*Ir complex

(Chemical Equation Presented) A new catalytic system for β-alkylation of secondary alcohols has been developed. In the presence of [Cp*IrCl 2]2 (Cp* = pentamethylcyclopentadienyl) catalyst and base, the reactions of various secondary alcohols with primary alcohols give β-alkylated higher alcohols in good to excellent yields without any hydrogen acceptor or hydrogen donor. This reaction proceeds via successive hydrogen-transfer reactions and aldol condensation.

Ruthenium-catalyzed β-alkylation of secondary alcohols with primary alcohols

The catalytic properties of a series of ruthenium complexes for β-alkylation of secondary alcohols with primary alcohols were studied. The catalytic activities of the ruthenium complexes were found to be dependent on the auxiliary ligands. The most active catalytic precursor found in this study is the ruthenium complex RuCl2(PPh3)2(2-NH2CH2Py) [2-NH2CH2Py = 2-aminomethyl pyridine], which effectively catalyzed the β-alkylation of both aryl- and alkyl-substituted secondary alcohols with benzylic and alkyl primary alcohols.

Iridium(I)-Catalyzed C-C and C-N Bond Formation Reactions via the Borrowing Hydrogen Strategy

Iridium(I) complexes having an imidazol-2-ylidene ligand with benzylic wingtips efficiently catalyzed the β-alkylation of secondary alcohols with primary alcohols and acceptorless dehydrogenative cyclization of 2-aminobenzyl alcohol with ketones through a borrowing hydrogen pathway. The β-alkylated alcohols, including cholesterol derivatives, and substituted quinolines were obtained in good yields by using a minute amount of the catalyst with a catalytic amount of NaOH or KOH under the air atmosphere, liberating water (and H2 in the case of quinoline synthesis) as the sole byproduct. Notably, this system demonstrated turnover numbers of 940 000 (for β-alkylation of secondary alcohols with primary alcohols by using down to 0.0001 mol % = 1 ppm of the catalyst) and 9200 (acceptorless dehydrogenative cyclization of 2-aminobenzyl alcohol with ketones).

Synthesis and Reactivity of Metal-Ligand Cooperative Bifunctional Ruthenium Hydride Complexes: Active Catalysts for β-Alkylation of Secondary Alcohols with Primary Alcohols

Three unsymmetrical NNN ligands with a 2-hydroxypyridyl fragment were used to react with RuHCl(PPh3)3(CO), affording the three bidentate ruthenium hydride complexes [(R1-C5H3N-CH2-C5H3N-C5H3N-R2)RuH(PPh3)2(CO)][Cl] (R1 = R2 = OH, 2a; R1 = OH, R2 = H, 2b; R1 = H, R2 = OH, 2c), respectively. When 2a,b were treated with t-BuOK, the two tridentate products [(O-C5H3N-CH2-C5H3N-C5H3N-R2)RuH(PPh3)(CO)] (R2 = OH, 3a; R2 = H, 3b) were obtained, via selective deprotonation of the -OH group of PyCH2PyOH moiety, indicating that this -OH group is more acidic than that of the PyPyOH moiety. The reaction of 2c with t-BuOK generated the bidentate product [(C5H4N-CH2-C5H3N-C5H3N-O)RuH(PPh3)2(CO)] (3c) and the tridentate product [(C5H4N-CH2-C5H3N-C5H3N-O)RuH(PPh3)(CO)] (3d). 3d could be further transformed to the diruthenium complex [(C5H4N-CH-C5H3N-C5H3N-O)Ru(PPh3)(CO)]2 (3e) via C-H activation of the -CH2- group in boiling toluene. The catalytic activity for β-alkylation of secondary alcohols with primary alcohols of these eight ruthenium complexes was tested, and the bidentate complexes 2c and 3c exhibit the highest activity. Complex 3c can be regarded as the intermediate of 2c. These results are important for developing more efficient bifunctional catalysts for such reactions.

Electronically tuneable orthometalated RuII–NHC complexes as efficient catalysts for C–C and C–N bond formations via borrowing hydrogen strategy

The catalytic activities of a series of simple and electronically tuneable cyclometalated RuII–NHC complexes (2a–d) were explored in various C–C/N bond formations following the borrowing hydrogen process. Slight modifications in the ligand backbone were noted to tune the activities of these complexes. Among them, the complex 2d featuring a 1,2,4-triazolylidene donor with a 4-NO2–phenyl substituent displayed the highest activity for the coupling of diverse secondary and primary alcohols with a low catalyst loading of 0.01 mol% and a sub-stoichiometric amount of inexpensive KOH base. The efficacy of this simple system was further showcased in the challenging one-pot unsymmetrical double alkylation of secondary alcohols using different primary alcohols. Moreover, the complex 2d also effectively catalyses the selective mono-N-methylation of various aromatic and aliphatic primary amines using methanol to deliver a range of N-methyl amines. Mechanistically, the β-alkylation reaction follows a borrowing hydrogen pathway which was established by the deuterium labelling experiment in combination with various control experiments. Intriguingly, in situ1H NMR and ESI-MS analyses evidently suggested the involvement of a Ru–H species in the catalytic cycle and further, the kinetic studies revealed a first order dependence of the reaction rate on the catalyst as well as the alcohol concentrations.

One pot tandem dual CC and CO bond reductions in the β-alkylation of secondary alcohols with primary alcohols by ruthenium complexes of amido and picolyl functionalized N-heterocyclic carbenes

Two different classes of ruthenium complexes, namely, [1-mesityl-3-(2,6-Me2-phenylacetamido)-imidazol-2-ylidene]Ru(p-cymene)Cl (1c) and {[1-(pyridin-2-ylmethyl)-3-(2,6-Me2-phenyl)-imidazol-2-ylidene]Ru(p-cymene)Cl}Cl (2c), successfully catalyzed the one-pot tandem alcohol-alcohol coupling reactions of a variety of secondary and primary alcohols, in moderate to good yields of ca. 63-89%. The mechanistic investigation performed on two representative catalytic substrates, 1-phenylethanol and benzyl alcohol using the neutral ruthenium (1c) complex showed that the catalysis proceeded via a partially reduced CC hydrogenated carbonyl species, [PhCOCH2CH2Ph] (3′), to the fully reduced CO and CC hydrogenated secondary alcohol, [PhCH(OH)CH2CH2Ph] (3). Furthermore, the time dependent study showed that the major product of the catalysis modulated between (3′) and (3) during the catalysis run performed over an extended period of 120 hours. Finally, the practical utility of the alcohol-alcohol coupling reaction was demonstrated by preparing five different flavan derivatives (13-17) related to various bioactive flavonoid natural products, in a one-pot tandem fashion.