62723-07-3

Upstream product

• 104-85-8 para-methylbenzonitrile 
• 703-55-9 1-naphthylmagnesiumbromide 
• 91-20-3 naphthalene 
• 874-60-2 4-methyl-benzoyl chloride 
• 108-88-3 toluene 
• 201230-82-2 carbon monoxide 
• 624-31-7 4-tolyl iodide 
• 90-14-2 1-Iodonaphthalene 
• 104-87-0 4-methyl-benzaldehyde 
• 5720-05-8 4-methylphenylboronic acid 
• 13922-41-3 1-Naphthylboronic acid 
• 13939-06-5 molybdenum hexacarbonyl 
• 99-94-5 p-Toluic acid 
• 3128-42-5 S-phenyl 4-methylbenzothioate 

Downstream Products

• 69295-75-6 α-(4-methylphenyl)-1-naphthalenemethanol 

Relevant academic research and scientific papers

Catalytic Aldehyde and Alcohol Arylation Reactions Facilitated by a 1,5-Diaza-3,7-diphosphacyclooctane Ligand

We report a catalytic method to access secondary alcohols by the coupling of aryl iodides. Either aldehydes or alcohols can be used as reaction partners, making the transformation reductive or redox-neutral, respectively. The reaction is mediated by a Ni catalyst and a 1,5-diaza-3,7-diphosphacyclooctane. This P2N2ligand, which has previously been unrecognized in cross-coupling and related reactions, was found to avoid deleterious aryl halide reduction pathways that dominate with more traditional phosphines and NHCs. An interrupted carbonyl-Heck type mechanism is proposed to be operative, with a key 1,2-insertion step forging the new C-C bond and forming a nickel alkoxide that may be turned over by an alcohol reductant. The same catalyst was also found to enable synthesis of ketone products from either aldehydes or alcohols, demonstrating control over the oxidation state of both the starting materials and products.

Carboxyboronate as a Versatile In Situ CO Surrogate in Palladium-Catalyzed Carbonylative Transformations

The application of carboxy-MIDA-boronate (MIDA=N-methyliminodiacetic acid) as an in situ CO surrogate for various palladium-catalyzed transformations is described. Carboxy-MIDA-boronate was previously shown to be a bench-stable boron-containing building block for the synthesis of borylated heterocycles. The present study demonstrates that, in addition to its utility as a precursor to heterocycle synthesis, carboxy-MIDA-boronate is an excellent in situ CO surrogate that is tolerant of reactive functionalities such as amines, alcohols, and carbon-based nucleophiles. Its wide functional-group compatibility is highlighted in the palladium-catalyzed aminocarbonylation, alkoxycarbonylation, carbonylative Sonogashira coupling, and carbonylative Suzuki–Miyaura coupling of aryl halides. A variety of amides, esters, (hetero)aromatic ynones, and bis(hetero)aryl ketones were synthesized in good-to-excellent yields in a one-pot fashion.

Tetra- And Dinuclear Palladium Complexes Based on a Ligand of 2,8-Di-2-pyridinylanthyridine: Preparation, Characterization, and Catalytic Activity

Complexation of L [L = 5-phenyl-2,8-di-2-pyridinyl-anthyridine] with [Pd(CH3CN)4](BF4)2 and [Pd(CH3CN)3Cl](BF4) in a molar ratio of 1:2 rendered the corresponding dinuclear complexes [Pd2L (CH3CN)4](BF4)4 (1) and [Pd2L (CH3CN)2Cl2](BF4)2 (2), respectively. However, treatment of L with (COD)PdCl2 followed by anion exchange yielded a tetranuclear complex [Pd4L3Cl4](PF6)4(4a). Structures of these complexes are characterized by both spectroscopy and X-ray crystallography. Interconversion of these three complexes was studied via the manipulation of stoichiometric ratio of ligand to metal precursor. The catalytic activity of these complexes for carbonylative Suzuki-Miyaura cross-coupling was investigated. Complex 2 shows an excellent catalytic activity on the reaction of aryl iodide with arylboronic acid in the presence of atmospheric pressure of CO to give the corresponding benzophenones.

Pd-NHC catalysed Carbonylative Suzuki coupling reaction and its application towards the synthesis of biologically active 3-aroylquinolin-4 (1H)-one and acridone scaffolds

We have unfolded a convenient and mild protocol for the synthesis of diaryl ketones via Pd- NHC catalysed carbonylative Suzuki coupling reaction. Notably, this method offers advantages like no use of toxic CO gas, shorter reaction time, high yield, and broad substrate scope. Several sensitive functional groups (like-COMe, -COOMe, -F, -Cl, -Br, -NH2, -CN) are well tolerated in this reaction. In addition, we have also demonstrated a new efficient route for the synthesis of biologically active and pharmaceutically important 2-substituted 3-Aroylquinolin-4(1H)-ones and acridone scaffolds.

A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation

The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.

TBHP-promoted direct oxidation reaction of benzylic Csp3-H bonds to ketones

A metal-free oxidation system employing tert-butyl hydroperoxide (TBHP) has been developed for selective oxidation of structurally diverse benzylic sp3 C-H bonds. This low-cost methodology allows for rapid generation of synthetically and biologically valued arylketones in good to excellent yields from readily available alkylarenes and diarylmethanes.

A synthesis of biaryl ketones via the C–S bond cleavage of thiol ester by a Cu/Ag salt

We report the synthesis of biaryl ketones via an unprecedented copper/silver catalyzed acylative cross-coupling of thiol esters with either an arylboronic acid or a potassium aryltrifluoroborate. This new method proceeds without a requisite Pd-catalyst and Cu(I)TC mediator, and is efficient, versatile, operationally simple, and accommodating functionally diverse thiol esters, arylboronic acids, and potassium aryltrifluoroborates.

Transition metal-free Suzuki type cross-coupling reaction for the synthesis of dissymmetric ketones

A simple, efficient and metal-free route for the synthesis of dissymmetric ketones through Suzuki type cross-coupling reaction has been established. This strategy signifies an attractive, cost-effective and operationally convenient tool for the synthesis of a wide range of dissymmetric ketones. Although conventional routes for the synthesis of ketones have been widely used, the potential challenge with these methods is functional group tolerance. The reported metal-free method represents a reaction with moderate functional group tolerance. The procedure is operationally convenient and shows broad substrate scope with good to excellent product yields.

KOtBu-Promoted Oxidation of (Hetero)benzylic Csp3-H to Ketones with Molecular Oxygen

An efficient and practical (hetero)benzylic sp3 C-H oxidation method has been developed. Notably, this user-friendly protocol employs inexpensive potassium tert-butoxide (KOtBu) as a promoter and proceeds under mild conditions using oxygen as the oxidant. A large variety of oxidation products were prepared in good to excellent yields. The utility of this "green" methodology was further demonstrated by the scale-up preparation of a biologically valued molecule.

KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki-Miyaura cross-coupling

This work reports a cost-effective and sustainable protocol for the carbonylative Suzuki-Miyaura cross-coupling reaction catalyzed by palladium nanoparticles (Pd NPs) supported on fibrous nanosilica (KCC-1). Under mild reaction conditions, the KCC-1-PEI/Pd catalytic system showed a turnover number (TON) 28-times and a turnover frequency (TOF) 51-times higher than the best supported Pd catalyst reported in the literature for the carbonylative cross-coupling between 4-iodoanisole and phenylboronic acid, as a test reaction. Also, the catalyst could be recycled up to ten times with a marginal loss in activity after the eighth cycle. The high activity of the catalyst can be attributed to the fibrous nature of the KCC-1 support and PEI functionalization provided the enhanced stability.