83135-69-7

Upstream product

• 103-63-9 1-phenyl-2-bromoethane 
• 529-20-4 2-methylphenyl aldehyde 
• 104-53-0 3-phenyl-propionaldehyde 
• 16419-60-6 2-Methylphenylboronic acid 
• 7294-50-0 tri-o-tolylboroxine 
• 13565-43-0 1-(2-methyl-phenyl)-3-phenyl-2-propen-1-one 
• 93433-65-9 1-(2-methylphenyl)-3-phenyl-1-propanone 
• 100-51-6 benzyl alcohol 
• 13565-43-0 (2E)-1-(2-methylphenyl)-3-phenyl-2-propenyl-1-one 
• 577-16-2 2-Methylacetophenone 
• 7287-82-3 1-O-tolyl-ethanol 
• 100-52-7 benzaldehyde 

Downstream Products

• 83135-54-0 (E)-1-methyl-2-(3-phenylprop-1-en-1-yl)benzene 

Relevant academic research and scientific papers

Selective C-alkylation Between Alcohols Catalyzed by N-Heterocyclic Carbene Molybdenum

The first implementation of a molybdenum complex with an easily accessible bis-N-heterocyclic carbene ligand to catalyze β-alkylation of secondary alcohols via borrowing-hydrogen (BH) strategy using alcohols as alkylating agents is reported. Remarkably high activity, excellent selectivity, and broad substrate scope compatibility with advantages of catalyst usage low to 0.5 mol%, a catalytic amount of NaOH as the base, and H2O as the by-product are demonstrated in this green and step-economical protocol. Mechanistic studies indicate a plausible outer-sphere mechanism in which the alcohol dehydrogenation is the rate-determining step.

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.

Room-Temperature Guerbet Reaction with Unprecedented Catalytic Efficiency and Enantioselectivity

We report herein an unprecedented highly efficient Guerbet-type reaction at room temperature (catalytic TON up to >6000). This β-alkylation of secondary methyl carbinols with primary alcohols has significant advantage of delivering higher-order secondary alcohols in an economical, redox-neutral fashion. In addition, the first enantioselective Guerbet reaction has also been achieved using a commercially available chiral ruthenium complex to deliver secondary alcohols with moderate yield and up to 92 % ee. In both reactions, the use of a traceless ketone promoter proved to be beneficial for the catalytic efficiency.

Reaction condition controlled nickel(ii)-catalyzed C-C cross-coupling of alcohols

The challenge in the C-C cross-coupling of secondary and primary alcohols using acceptorless dehydrogenation coupling (ADC) is the difficulty in accurately controlling product selectivities. Herein, we report a controlled approach to a diverse range of β-alkylated secondary alcohols, α-alkylated ketones and α,β-unsaturated ketones using the ADC methodology employing a Ni(ii) 4,6-dimethylpyrimidine-2-thiolate cluster catalyst under different reaction conditions. This catalyst could tolerate a wide range of substrates and exhibited a high activity for the annulation reaction of secondary alcohols with 2-aminobenzyl alcohols to yield quinolines. This work is an example of precise chemoselectivity control by careful choice of reaction conditions.

Manganese-Catalyzed β-Alkylation of Secondary Alcohols with Primary Alcohols under Phosphine-Free Conditions

Manganese(I) complexes bearing a pyridyl-supported pyrazolyl-imidazolyl ligand efficiently catalyzed the direct β-alkylation of secondary alcohols with primary alcohols under phosphine-free conditions. The β-alkylated secondary alcohols were obtained in moderate to good yields with water formed as the byproduct through a borrowing hydrogen pathway. β-Alkylation of cholesterols was also effectively achieved. The present protocol provides a concise atom-economical method for C-C bond formation from primary and secondary alcohols.

Synthesis and catalytic applications of ruthenium(ii)-phosphino-oxime complexes

In this work, the preparation of the first ruthenium complexes containing a phosphino-oxime ligand is presented. Thus, the reaction of cis-[RuCl2(DMSO)4] (3) with 2.4 equivalents of 2-Ph2PC6H4CH=NOH (1) in refluxing THF led to the clean formation of the octahedral ruthenium(ii) derivative cis,cis,trans-[RuCl2{κ2-(P,N)-2-Ph2PC6H4CH=NOH}2] (5), whose structure was unambiguously confirmed by means of a single-crystal X-ray diffraction study. Complex 5 could also be synthesized from the reaction of the dimer [{RuCl(μ-Cl)(η6-p-cymene)}2] (4) with an excess of 1 in refluxing toluene. Treatment of 4 with 2 equivalents of 1, in CH2Cl2 at r.t., allowed also the preparation of the half-sandwich Ru(ii) derivative [RuCl{κ2-(P,N)-2-Ph2PC6H4CH=NOH}(η6-p-cymene)][PF6] (6). In addition, complexes 5 and 6 proved to be active catalysts for the rearrangement of aldoximes to primary amides, as well as for the α-alkylation/reduction of acetophenones with primary alcohols, with the former showing the best performances in both processes.

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.

A base-controlled chemoselective transfer hydrogenation of α,β-unsaturated ketones catalyzed by [IrCpCl2]2 with 2-propanol

A simple homogeneous catalyst system based on commercially available [IrCpCl2]2 has been developed for the conjugate reduction of α,β-unsaturated ketones. Under the optimized conditions, a wide range of α,β-unsaturated ketones were reduced to saturated ketones in 83-98% yield. While switching the base from K2CO3 to KOH, saturated alcohols was selectively obtained.

Strategic Application and Transformation of ortho-Disubstituted Phenyl and Cyclopropyl Ketones to Expand the Scope of Hydrogen Borrowing Catalysis

The application of an iridium-catalyzed hydrogen borrowing process to enable the formation of α-branched ketones with higher alcohols is described. In order to facilitate this reaction, ortho-disubstituted phenyl and cyclopropyl ketones were recognized as crucial structural motifs for C-C bond formation. Having optimized the key catalysis step, the ortho-disubstituted phenyl products could be further manipulated by a retro-Friedel-Crafts acylation reaction to produce synthetically useful carboxylic acid derivatives. In contrast, the cyclopropyl ketones underwent homoconjugate addition with several nucleophiles to provide further functionalized branched ketone products.

Efficient iron-catalyzed direct β-alkylation of secondary alcohols with primary alcohols

The efficient iron-catalyzed direct β-alkylation of secondary alcohols with primary alcohols is described. In the presence of the commercially available iron catalyst (ferrocenecarboxaldehyde, 1b) and a catalytic amount of base, the reactions give β-alkylated higher alcohols in high yields in the absence of any sacrificial agents (hydrogen acceptors or hydrogen donors) and nitrogen or phosphorus ligands. For the first time, iron is employed as an inexpensive and environmentally benign alternative with high atom efficiency to noble metal-based catalysts in this type of reaction. Copyright