1334532-07-8

Upstream product

• 27798-60-3 methyl 2-(2-methoxyphenyl)acetate 
• 22979-35-7 Methyl phenyldiazoacetate 
• 100-66-3 methoxybenzene 
• 108-95-2 phenol 
• 934-56-5 trimethyl(phenyl)stannane 
• 347187-58-0 methyl α-diazo-α-(2-methoxyphenyl)acetate 

Relevant academic research and scientific papers

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.

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.

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

(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.

Rhodium-catalyzed cross-coupling reaction of arylboronates and diazoesters and tandem alkylation reaction for the synthesis of quaternary r,r-heterodiaryl carboxylic esters

A rhodium-catalyzed one-pot three-component coupling reaction was developed for the synthesis of quaternary α,α-heterodiaryl carboxylic esters. This reaction involves cross-coupling of the arylrhodium(I) complexes with R-aryldiazoacetates to form oxa-π-al