384365-48-4

Upstream product

• 53088-69-0 methyl 3-methylphenylacetate 
• 621-36-3 m-methylphenylacetic acid 

Downstream Products

• 136125-68-3 methyl 3-methylphenylglyoxylate 
• 1152170-61-0 methyl 2-hydroxy-2-m-tolylacetate 
• 1070980-29-8 methyl (2S,3S)-2-benzyloxy-3-hydroxy-3-phenyl-2-(m-tolyl)propanoate 
• 1070980-30-1 methyl (2S,3S)-2-benzyloxy-3-hydroxy-3-(4-methoxyphenyl)-2-(m-tolyl)propanoate 
• 1070980-31-2 methyl (2S,3S)-2-benzyloxy-3-(4-bromophenyl)-3-hydroxy-2-(m-tolyl)propanoate 
• 1301262-67-8 (5R,11S,14S)-methyl 2,8-dimethyl-14-(m-tolyl)-6,12-dihydro-5,11-ethanodibenzo[b,f][1,5]diazocine-14-carboxylate 
• 1313370-84-1 methyl 2-methyl-3-phenyl-1-(m-tolyl)cycloprop-2-enecarboxylate 
• 1351619-57-2 methyl 2-(1-benzyl-1H-indol-3-yl)-2-m-tolylacetate 
• 1385029-82-2 (S)-methyl 2-methyl-3-phenyl-1-(m-tolyl)cycloprop-2-enecarboxylate 
• 1416804-11-9 methyl 1-benzyl-3-oxo-2-(m-tolyl)indoline-2-carboxylate 

Relevant academic research and scientific papers

B(C6F5)3-Catalyzed site-selective N1-alkylation of benzotriazoles with diazoalkanes

Alkylation of benzotriazoles is synthetically challenging, often leading to mixtures of N1 and N2 alkylation. Herein, metal-free catalytic site-selective N1-alkylation of benzotriazoles with diazoalkanes is described in the presence of 10 mol% of B(C6F5)3. These reactions provide N1-alkylated benzotriazoles in good to excellent yields and this protocol is successfully adapted to gram-scale syntheses as well as a derivative with antimicrobial activity.

Access to Bromo-γ-butenolides via Zwitterion-Catalyzed Rearrangement of Cyclopropene Carboxylic Acids

γ-Butenolides are useful structural motifs in many pharmaceutically relevant compounds. In particular, halogenated γ-butenolides are attractive building blocks because the halogen handles can readily be manipulated to give various functional molecules. In

Diazo Activation with Diazonium Salts: Synthesis of Indazole and 1,2,4-Triazole

A donor/acceptor diazo activation strategy, processing via condensation using diazonium salts without the addition of any other catalysts or reagents, is reported. The diazenium intermediate was found to undergo cyclization to give indazoles in excellent yields. Alternatively, in the presence of nitriles, substituted 1,2,4-triazoles were obtained in good to excellent yields. This interesting diazenium route provides a new approach to achieve complex heterocycle synthesis under mild conditions.

Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of Polysubstituted Butadienes and Macrocyclic P-glycoprotein Inhibitors

The efficient and stereoselective synthesis of polysubstituted butadienes, especially the multifunctional butadienes, represents a great challenge in organic synthesis. Herein, we wish to report a distinctive Pd(0) carbene-initiated decarboxylative olefination approach that enables the direct coupling of diazo esters with vinylethylene carbonates (VECs), vinyl oxazolidinones, or vinyl benzoxazinones to afford alcohol-, amine-, or aniline-containing 1,3-dienes in moderate to high yields and with excellent stereoselectivity. This protocol features operational simplicity, mild reaction conditions, a broad substrate scope, and gram-scalability. Notably, a structurally unique allylic Pd(II) intermediate was isolated and characterized. DFT calculation and control experiments demonstrated that a rare Pd(0) carbene intermediate could be involved in this reaction. Moreover, the polysubstituted butadienes as novel building blocks were unprecedentedly assembled into macrocycles, which efficiently inhibited the P-glycoprotein and dramatically reversed multidrug resistance in cancer cells by 190-fold.

Cobalt(III)-Catalyzed Directed C-H Coupling with Diazo Compounds: Straightforward Access towards Extended π-Systems

The first highly efficient and scalable cobalt-catalyzed directed C-H functionalization with carbene precursors is presented. This methodology provides a modular route towards a new class of conjugated polycyclic hydrocarbons with tunable emission wavelengths both in solution and in the solid state.

Copper(II)-acid catalyzed cyclopropanation of 1,3-dienamides by electrophilic activation of α-aryl diazoesters

Copper(II)-acid catalyzed cyclopropanation of electron-rich alkenes, such as 1,3-dienamides, with α-aryl diazoesters are described. The reaction could be performed without rare metal catalysts, excess substrate, or the need for the slow addition of the diazoesters.

An efficient synthesis of aryl α-keto esters

A new one-pot approach for the synthesis of aryl α-keto ester based on the diazo transfer and oxidation of diazo group is developed.

Computational and experimental studies of the effect of substituents on the singlet-triplet energy gap in phenyl(carbomethoxy)carbene

The effect of aromatic substitution on the singlet-triplet energy gap in substituted phenyl-(carbomethoxy)carbene (X-Ph-C-CO2CH3, PCC) has been explored by time-resolved infrared (TRIR) spectroscopy and gas-phase computational methods. The ground state of para-substituted PCC is calculated to change from the triplet state in p-NO2-PCC (AGST = 6.1 kcal/mol) to the singlet state in p-NH2-PCC (AGST = -2.81kcal/mol). The absence of solvent perturbation in the TRIR spectra of p-N(CH3)2-PCC (which should have electronic properties similar to p-NH2-PCC) and parent PCC is consistent with their ground states lying >±2 kcal/mol from the next available electronic state, in line with the computational results. The observation of solvent perturbation in the TRIR spectra ofp-OCH3-PCC and p-CH3-PCC implies that their ground states lie ST values of -3.9 and -1.3 kcal/mol from polarizable continuum model (PCM) calculations with acetonitrile as a solvent. Gas-phase computational results for the meta- and ortho-substituted PCC species are also presented, along with selected linear free energy (LFE) relationships for the para and meta species.

A kinetic study on the pairwise competition reaction of α-diazo esters with rhodium(II) catalysts: Implication for the mechanism of Rh(II)-carbene transfer

The relative rate constants for the Rh(II)-mediated diazo decomposition of a series of para- or mete-substituted diazophenylacetates were measured through intermolecular competition. The kinetic data were further subjected to Hammett correlation analysis