622860-35-9

Upstream product

• 644-34-8 (E)-3-(benzo[d][1,3]dioxol-5-yl)-1-phenylprop-2-en-1-one 
• 30830-55-8 3-(3,4-methylenedioxyphenyl)propionaldehyde 
• 495-76-1 piperonol 
• 98-85-1 1-Phenylethanol 
• 7031-03-0 3-(benzo[d][1,3]dioxol-5-yl)propan-1-ol 
• 6258-37-3 <3,4-(methylenedioxy)phenyl>propargyl alcohol 
• 64-17-5 ethanol 

Downstream Products

• 864758-71-4 5-benzo[1,3]dioxol-5-yl-3-phenylpent-1-yn-3-ol 

Relevant academic research and scientific papers

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.

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.

Switchable β-alkylation of secondary alcohols with primary alcohols by a well-defined cobalt catalyst

β-alkylation of secondary alcohols with primary alcohols to selectively generate alcohols by a well-defined Co catalyst is presented. Remarkably, a low catalyst loading of 0.7 mol % can be employed for the reaction. More significantly, this study represents the first Co-catalyzed switchable alcohol/ketone synthesis by simply manipulating the reaction parameters. In addition, the transformation is environmentally friendly, with water as the only byproduct.

Transition metal complexes of a bis(carbene) ligand featuring 1,2,4-triazolin-5-ylidene donors: structural diversity and catalytic applications

Dialkylation of the 1,3-bis(1,2,4-triazol-1-yl)benzene with ethyl bromide results in the formation of [L-H2]Br2which, upon salt metathesis with NH4PF6, readily yields the bis(triazolium) salt [L-H2](PF6)2with non-coordinating counterions. [L-H2](PF6)2and Ag2O react in a 1?:?1 ratio to yield a binuclear AgI-tetracarbene complex of the composition [(L)2Ag2](PF6)2which undergoes a facile transmetalation reaction with [Cu(SMe2)Br] to deliver the corresponding CuI-NHC complex [(L)2Cu2](PF6)2. In contrast, the [L-H2]Br2reacts with [Ir(Cp*)Cl2]2to generate a doubly C-H activated IrIII-NHC complex5. Similarly, the triazolinylidene donor supported diorthometalated RuII-complex6is also obtained. Complexes5and6represent the first examples of a stable diorthometalated binuclear IrIII/RuII-complex supported by 1,2,4-triazolin-5-ylidene donors. The synthesized IrIII-NHC complex5is found to be more effective than its RuII-analogue (6) for the reduction of a range of alkenes/alkynesviathe transfer hydrogenation strategy. Conversely, RuII-complex6is identified as an efficient catalyst (0.01 mol% loading) for the β-alkylation of a wide range of secondary alcohols using primary alcohols as alkylating partnersviaa borrowing hydrogen strategy.

C-Alkylation of Secondary Alcohols by Primary Alcohols through Manganese-Catalyzed Double Hydrogen Autotransfer

A new Mn-catalyzed alkylation of secondary alcohols with non-activated alcohols is presented. The use of a stable and well-defined manganese pincer complex, stabilized by a PNN ligand, together with a catalytic amount of base enabled the conversion of renewable alcohol feedstocks to a broad range of higher-value alcohols in good yields with water as the sole byproduct. The strategy eliminates the need for exogenous and detrimental alkyl halides as well as the use of noble metal catalysts, making the C-alkylation through double hydrogen autotransfer a highly sustainable and environmentally benign process. Mechanistic investigations support a hydrogen autotransfer mechanism in which a non-innocent ligand plays a crucial role.

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.

Tandem Cross Coupling Reaction of Alcohols for Sustainable Synthesis of β-Alkylated Secondary Alcohols and Flavan Derivatives

A Ru(II) NHC complex (loading down to 0.001 mol%) catalyzed cross coupling of a broad range of aromatic, aliphatic and heterocyclic alcohols is reported. This protocol also functioned efficiently under solvent-free conditions. Remarkably, this catalytic system disclosed so far the highest TON of 288000 for the cross coupling of alcohols. Notably, this methodology was successfully applied for the one-pot synthesis of a range of flavan derivatives. A detailed DFT studies and kinetic experiments were performed to understand the reaction mechanism as well as the high reactivity of this catalytic system. (Figure presented.).

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.

Bimetallic Pt–Sn/γ-Al2O3catalyzed β-alkylation of secondary alcohols with primary alcohols under solvent-free conditions

Heterogeneous bimetallic Pt–Sn/γ-Al2O3(0.5?wt% Pt, molar ratio Pt:Sn?=?1:3) was successfully utilized as the catalyst for direct β-alkylation of secondary alcohols with primary alcohols under solvent-free conditions. β-Alkylated secondary alcohols were obtained in moderate to high yields with water formed as the by-product through a hydrogen borrowing pathway. The present protocol provides a concise atom-economical and environmentally benign method for C–C bond formation.

Ruthenium-catalyzed cycloisomerization of cis-3-en-1-ynes to cyclopentadiene and related derivatives through a 1,5-sigmatropic hydrogen shift of ruthenium vinylidene intermediates

We report a new ruthenium-catalyzed cycloisomerization of unactivated cis-3-en-1-ynes, which produces substituted cyclopentadiene and related derivatives. The mechanism of this cyclization is proposed to involve a [1,5]-sigmatropic hydrogen shift of ruthenium-vinylidene intermediates on the basis of deuterium-labeling experiments. Copyright