19048-84-1

Upstream product

• 135-02-4 ortho-anisaldehyde 
• 579-75-9 2-Methoxybenzoic acid 
• 612-16-8 (2-methoxyphenyl)methanol 
• 21615-34-9 2-Methoxybenzoyl chloride 
• 578-58-5 2-methylmethoxybenzene 

Relevant academic research and scientific papers

Aldehyde effect and ligand discovery in Ru-catalyzed dehydrogenative cross-coupling of alcohols to esters

The presence of different aldehydes is found to have a significant influence on the catalytic performance when using PN(H)P type ligands for dehydrogenation of alcohols. Accordingly, hybrid multi-dentate ligands were discovered based on an oxygen-transfer alkylation of PNP ligands by aldehydes. The relevant Ru-PNN(PO) system provided the desired unsymmetrical esters in good yields via acceptorless dehydrogenation of alcohols. Hydrogen bonding interactions between the phosphine oxide moieties and alcohol substrates likely assisted the observed high chemoselectivity.

Rhodium-catalyzed synthesis of imines and esters from benzyl alcohols and nitroarenes: Change in catalyst reactivity depending on the presence or absence of the phosphine ligand

The [Rh(COD)Cl]2/xantphos/Cs2CO3 system efficiently catalyzes the reductive N-alkylation of aryl nitro compounds with alcohols by a borrowing-hydrogen strategy to afford the corresponding imine products in good to excellent yields. In the absence of xantphos, the [Rh(COD)Cl]2/Cs2CO3 catalytic system behaves as an effective catalyst for the dehydrogenative coupling of alcohols to esters, with nitrobenzene as a hydrogen acceptor. The reactivity of the rhodium catalytic system can be easily manipulated to selectively afford the imine or ester.

Manganese Pincer Complexes for the Base-Free, Acceptorless Dehydrogenative Coupling of Alcohols to Esters: Development, Scope, and Understanding

Aliphatic PNP pincer-supported earth-abundant manganese(I) dicarbonyl complexes behave as effective catalysts for the acceptorless dehydrogenative coupling of a wide range of alcohols to esters under base-free conditions. The reaction proceeds under neat conditions, with modest catalyst loading and releasing only H2 as byproduct. Mechanistic aspects were addressed by synthesizing key species related to the catalytic cycle (characterized by X-ray structure determination, multinuclear (1H, 13C, 31P, 15N, 55Mn) NMR, infrared spectroscopy, inter alia), by studying elementary steps connected to the postulated mechanism, and by resorting to DFT calculations. As in the case of related ruthenium and iron PNP catalysts, the dehydrogenation results from cycling between the amido and amino-hydride forms of the PNP-Mn(CO)2 scaffold. For the dehydrogenation of alcohols into aldehydes, our results suggest that the highest energy barrier corresponds to the hydrogen release from the amino-hydride form, although its value is close to that of the outer-sphere dehydrogenation of the alcohol into aldehyde. This contrasts with the ruthenium and iron catalytic systems, where dehydrogenation of the substrate into aldehyde is less energy-demanding compared to hydrogen release from the cooperative metal-ligand framework.

Formamides as Lewis Base Catalysts in SNReactions—Efficient Transformation of Alcohols into Chlorides, Amines, and Ethers

A simple formamide catalyst facilitates the efficient transformation of alcohols into alkyl chlorides with benzoyl chloride as the sole reagent. These nucleophilic substitutions proceed through iminium-activated alcohols as intermediates. The novel method, which can be even performed under solvent-free conditions, is distinguished by an excellent functional group tolerance, scalability (>100 g) and waste-balance (E-factor down to 2). Chiral substrates are converted with excellent levels of stereochemical inversion (99 %→≥95 % ee). In a practical one-pot procedure, the primary formed chlorides can be further transformed into amines, azides, ethers, sulfides, and nitriles. The value of the method was demonstrated in straightforward syntheses of the drugs rac-Clopidogrel and S-Fendiline.

Significant promoting effects of Lewis acidity on Au-Pd systems in the selective oxidation of aromatic hydrocarbons

An unprecedented synergistic effect, obtained for rationally designed Au-Pd alloy nanoparticles supported on an acidic metal-organic framework (MOF), in the aerobic oxidation of the primary C-H bonds in toluene and derivates is reported.

Solvent-free oxidation of primary carbon-hydrogen bonds in toluene using Au-Pd alloy nanoparticles

Selective oxidation of primary carbon-hydrogen bonds with oxygen is of crucial importance for the sustainable exploitation of available feedstocks. To date, heterogeneous catalysts have either shown low activity and/or selectivity or have required activated oxygen donors. We report here that supported gold-palladium (Au-Pd) nanoparticles on carbon or TiO2 are active for the oxidation of the primary carbon-hydrogen bonds in toluene and related molecules, giving high selectivities to benzyl benzoate under mild solvent-free conditions. Differences between the catalytic activity of the Au-Pd nanoparticles on carbon and TiO2 supports are rationalized in terms of the particle/support wetting behavior and the availability of exposed corner/edge sites.

An in situ generated ruthenium catalyst for the Tishchenko reaction

A simple and efficient catalytic system for the selective dimerization of aldehydes, the Tishchenko reaction, is described. High yields of symmetrical esters were generally achieved using an in situ generated ruthenium catalyst in association with the electron-rich and hindered cyclohexyl-(diphenyl)phosphane (CyPPh2) ligand.

Tunable bromomagnesium thiolate tishchenko reaction catalysts: Intermolecular aldehyde-trifluoromethylketone coupling

(Figure Presented) Applied knowledge: A new thiolate-catalyzed Tishchenko reaction inspired by biochemical processes features exceptionally good control over the catalyst's steric/electronic properties. The isolation of reaction intermediates provided valua-ble insights into the reaction mechanism, which in turn has allowed the development of the first cross-Tishchenko coupling reactions between aldehydes and activated ketones (see example).