5359-50-2

Upstream product

• 3262-89-3 triphenylboroxine 
• 22979-36-8 methyl 2-diazo-2-(4-methoxypheny)acetate 
• 22979-35-7 Methyl phenyldiazoacetate 
• 100-66-3 methoxybenzene 
• 98-80-6 phenylboronic acid 
• 5720-07-0 4-methoxyphenylboronic acid 
• 934-56-5 trimethyl(phenyl)stannane 
• 108-95-2 phenol 
• 13139-86-1 4-methoxyphenyl magnesium bromide 
• 928712-61-2 α-Hydroxy-4-methoxy-α-phenylbenzeneacetic acid methyl ester 
• 15206-55-0 methyl 2-oxo-2-phenylacetate 
• 101-41-7 benzeneacetic acid methyl ester 
• 104-01-8 4-Methoxyphenylacetic acid 
• 23786-14-3 4-methoxy-phenyl acetic acid methyl ester 

Downstream Products

• 54775-13-2 1-(4-hydroxyphenyl)-1-methoxycarbonyl-1-phenylmethane 

Relevant academic research and scientific papers

Br?nsted acid-catalyzed Friedel-Crafts-type alkylation of arenes with α-aryl diazoacetates

An efficient Br?nsted acid-catalyzed Friedel-Crafts-type alkylation of arenes with α-aryl diazoacetates has been developed. This protocol enables effective access to various highly functionalized diarylmethane derivatives in moderate to high yields. Moreo

Room Temperature Coupling of Aryldiazoacetates with Boronic Acids Enhanced by Blue Light Irradiation

A visible-light-promoted photochemical protocol is reported for the coupling of aryldiazoacetates with boronic acids. This photochemical reaction shows great enhancement compared to the same protocol performed in the absence of light. Except for a few cases, the room temperature coupling in the dark (thermal process) generally does not work. When it does, it is likely to also involve free carbenes as key intermediates. Alternatively, photochemical reactions show a broad scope, can be performed under air and tolerate a wide variety of functional groups. Reaction-evolution monitoring, DFT calculations and control experiments have been used to evaluate the main aspects of this intricate mechanistic scenario. Biologically active molecules Adiphenine, Benactyzine and Aprophen have been prepared as examples of synthetic applications.

Synthesis of Chiral Triarylmethanes Bearing All-Carbon Quaternary Stereocenters: Catalytic Asymmetric Oxidative Cross-Coupling of 2,2-Diarylacetonitriles and (Hetero)arenes

A direct and enantioselective oxidative cross-coupling of racemic 2,2-diarylacetonitriles with electron-rich (hetero)arenes has been described, which allows for efficient construction of triarylmethanes bearing all-carbon quaternary stereocenters with excellent chemo- and enantioselectivity. The reaction has an excellent functional group tolerance, and exhibits a broad scope with respect to both 2,2-diarylacetonitrile and (hetero)arene components. The rich chemistry of the cyano group allows for facile synthesis of other valuable chiral triarylmethanes bearing all-carbon quaternary centers that are otherwise difficult to access.

Mechanistic Insights into the Chemo- And Regio-Selective B(C6F5)3 Catalyzed C-H Functionalization of Phenols with Diazoesters

The Lewis acidic B(C6F5)3 was recently demonstrated to be effective for the C-H alkylation of phenols with diazoesters. The method avoids the general hydroxyl activation in transition-metal catalysis. Ortho-selective C-H alkylation occurs regardless of potential para-selective C-H alkylation and O-H alkylation. In the present study, a theoretical calculation was carried out to elucidate the reaction mechanism and the origin of chemo- and regio-selectivity. It is found that the previously proposed B(C6F5)3/N or B(C6F5)3/C bonding-involved mechanisms are not favorable, and a more favored one involves the B(C6F5)3/C=O bonding, rate-determining N2 elimination, selectivity-determining electrophilic attack, and proton transfer steps. Meanwhile, the new mechanism is consistent with KIE and competition experiments. The facility of the mechanism is attributed to two factors. First, the B(C6F5)3/C=O bonding reduces the steric hindrance during electrophilic attack. Second, the bonding forms the conjugated system by which the LUMO energy is reduced via the electron-withdrawing B(C6F5)3. The ortho-selectivity resulted from the greater ortho-C-C (than para-C-C) interaction and the O-H···O and O-H···F hydrogen-bond interaction during electrophilic attack. The greater C-C (than C-O) interaction and the π-πstacking between the benzene rings of phenol and diazoester concerted contribute to the chemo-selective C-H alkylation.

Palladium-Catalysed Cross-Coupling of Benzylammonium Salts with Boronic Acids under Mild Conditions

Herein, we give a full account of the development of the palladium-catalysed cross-coupling of benzylammonium salts with boronic acids. A range of benzylamine-derived quaternary ammonium salts can be coupled with boronic acids under relatively mild conditions. Our optimization has identified ligands that can be used to chemoselectively cross-couple at the ammonium in the presence of chlorides. We demonstrate that intramolecular palladium-catalysed C-H activation is also a viable pathway for the putative benzyl-Pd(II) intermediate obtained upon oxidative addition and have optimised this to obtain fluorene in good yield.

(C6F5)3B Catalyzed Chemoselective and ortho-Selective Substitution of Phenols with α-Aryl α-Diazoesters

The development of an efficient method for the site-selective substitution of unprotected phenols has long been considered as an attractive but challenging task. Herein, we describe a highly chemo- and ortho-selective substitution reaction of phenols with α-aryl α-diazoacetates with commercially available (C6F5)3B as the catalyst. This reaction proceeds under simple and mild conditions with high efficiency, it features a wide substrate scope and can be easily scaled up.

RhI-Catalyzed Stille-Type Coupling of Diazoesters with Aryl Trimethylstannanes

A RhI-catalyzed cross-coupling of diazoester with arylstannane was developed. This reaction represents the first Stille-type coupling that uses a diazo compound as the coupling partner. The reaction is operationally simple and can be carried out under mild conditions, thus providing an alternative approach for the synthesis of α-aryl esters. RhI-carbene migratory insertion process is suggested to be involved as the key step in this Stille-type coupling.

Rhodium catalyzed arylation of diazo compounds with aryl boronic acids

A general and efficient synthesis of diarylacetate, a diarylmethine derivative, was accomplished through rhodium catalyzed direct arylation of diazo compounds with arylboronic acids. The reaction tolerates various boronic acid derivatives and functional groups. Notably, chemoselective arylation of diazo compounds over other electrophiles were demonstrated. The efficacy of the developed methodology is shown by the expeditious synthesis of the core structure of diclofensine.

Chemoselective carbophilic addition of α-diazoesters through ligand-controlled gold catalysis

The chemoselective addition of arenes and 1,3-diketones to α-aryldiazoesters was achieved through ligand-controlled gold catalysis. Unlike a dirhodium catalyst (which promotes C sp 3-H insertion and cyclopropanation) and a copper catalyst (which catalyzes O-H and N-H insertions), the gold catalyst with an electron-deficient phosphite as the ancillary ligand exclusively gave the carbophilic addition product, thus representing a new and efficient approach to form carbophilic carbocations , which selectively react with carbon nucleophiles.

Copper(II)-acid co-catalyzed intermolecular substitution of electron-rich aromatics with diazoesters

The intermolecular aromatic substitution of N,N-dialkylanilines and alkoxybenzenes with diazoesters is shown to proceed in the presence of catalytic amounts of both copper(II) salt and acid (Lewis or Br?nsted). This method is a mild and rare metal-free C-C bond formation reaction between aromatic (sp2) and aliphatic (sp3) carbons.