90445-44-6

Upstream product

• 1018-97-9 2,2'-dimethylbenzophenone 
• 108-88-3 toluene 
• 119-67-5 o-carboxybenzaldehyde 
• 932-31-0 ortho-tolylmagnesium bromide 
• 601-70-7 3,3-dichlorophthalide 
• 21147-26-2 2-(2-methylbenzoyl)benzoic acid methyl ester 
• 529-20-4 2-methylphenyl aldehyde 
• 16419-60-6 2-Methylphenylboronic acid 
• 643-79-8 o-phthalic dicarboxaldehyde 
• 4122-56-9 methyl o-formylbenzoate 
• 7294-50-0 tri-o-tolylboroxine 
• 95-46-5 2-methylphenyl bromide 
• 80716-36-5 o-(o-Methylbenzyl)benzoic acid 
• 57271-91-7 N-butyl-2-hydroxybenzamide 

Downstream Products

• 502924-03-0 2-carboxy-2'-methyldiphenylmethyl methylsulfide 

Relevant academic research and scientific papers

Access to Diarylmethanols by Wittig Rearrangement of ortho-, meta-, and para-Benzyloxy- N-Butylbenzamides

The N-butyl amide group, CONHBu, has been found to be an effective promoter of the [1,2]-Wittig rearrangement of aryl benzyl ethers and thus allow the two-step synthesis of isomerically pure substituted diarylmethanols starting from simple hydroxybenzoic acid derivatives. The method is compatible with a wide range of functional groups including methyl, methoxy, and fluoro, although not with nitro and, unexpectedly, is applicable to meta as well as ortho and para isomeric series.

Efficient One-Pot Synthesis of 3-Substituted Phthalides via Additive Arylation of Organozinc Intermediate

In recent years, substitution at the third position on phthalides has been proven a valua-ble synthetic intermediate for developing active molecules. We reported a direct and efficient one-pot method for the synthesis of 3-aryl Phthalides performed by adding organo-zinc reagent on methyl-2-formylbenzoate; reagent formed in-situ by the reaction between diethylzinc and different aryl boronic acid derivatives without using any ligand. The possible mechanism involved a coordi-nated zinc carbonyl transition state, arylation, and followed by the intramolecular cyclization. The substituents groups in boronic having different electronic and steric properties played an important role in the reaction completion time and yield. The structure elucidation and confirmation of the synthesized compounds were done by using H-NMR analytical data. The method can be useful for synthesizing various scaffolds and intermediates in search of potentially active compounds.

Direct and selective synthesis of 3-arylphthalides via nickel-catalyzed aryl addition/intramolecular esterification

Herein we report a nickel-catalyzed aryl addition/intramolecular esterification in a cascade fashion. Under the combination of commercially available nickel precursor and tridentate ligand, the one pot protocol offers a direct, simple and regioselective approach to access 3-aryl phthalide derivatives from two readily available substrates with good efficiency, broad scope as well as satisfactory functional group compatibility.

Rhenium-Catalyzed Phthalide Synthesis from Benzamides and Aldehydes via C-H Bond Activation

The [4 + 1] annulation of benzamides and aldehydes for phthalide synthesis was achieved via rhenium-catalyzed C-H activation, which demonstrates an unprecedented reaction pattern distinct from those of other transition-metal catalyses. The reaction also features readily available starting materials, a wide scope for both electro-rich and electro-deficient substrates, and the elimination of homoannulation byproducts.

Catalytic asymmetric synthesis of 3-aryl phthalides enabled by arylation-lactonization of 2-formylbenzoates

The catalytic asymmetric synthesis of 3-aryl phthalides is reported through a sequential asymmetric arylation-lactonization reaction. The reaction is enabled by a boron-zinc exchange to generate reactive arylating agents, which react with 2-formylbenzoates in the presence of a chiral amino naphthol ligand. The enantiodetermining step is the arylation of the aldehyde, which then undergoes a lactonization event to yield the corresponding phthalides in good yields and enantioselectivities.

Scalable Electrochemical Dehydrogenative Lactonization of C(sp2/sp3)-H Bonds

A practical, electrochemical method is developed for the direct dehydrogenative lactonization of C(sp2/sp3)-H bonds under external oxidant- and metal-free conditions, delivering diverse lactones, including coumarin derivatives with excellent regioselectivity. The scalable nature of this newly developed electrochemical process was demonstrated on a 40 g scale following an operationally simple protocol. The remote lactonization of C(sp3)-H bonds would constitute an important synthetic advance toward electrochemical C-O bond formation.

Ruthenium-Catalyzed Enantioselective Hydrogenation/Lactonization of 2-Acylarylcarboxylates: Direct Access to Chiral 3-Substituted Phthalides

Highly enantioselective tandem hydrogenation/lactonization of various 2-acylarylcarboxylates including 2-aroylarylcarboxylates were realized by using [RuCl(benzene)(S)-SunPhos]Cl as the catalyst under mild reaction conditions. Excellent enantioselectivities (up to 99.6 % ee) and activities (S/C=1000) were obtained. This convenient and practical method enables a direct access to a series of highly optically pure 3-substituted phthalides that are very important molecules as valuable pharmacological compounds and diversified synthons for medicinal chemistry. Moreover, a gram-scale reaction was performed to further demonstrate the practicality of this approach.

Highly Diastereoselective Crown Ether Catalyzed Arylogous Michael Reaction of 3-Aryl Phthalides

The first arylogous Michael reaction of 3-aryl phthalides has been developed. The reaction, promoted by catalytic amounts of KOH or K3PO4 and dibenzo-18-crown-6, affords the corresponding 3,3-disubstituted phthalides in good to high

Hydrosilane and bismuth-accelerated palladium catalyzed aerobic oxidative esterification of benzylic alcohols with air

In a palladium-catalyzed oxidative esterification, hydrosilane can serve as an activator of palladium catalyst with bismuth, thus leading to a novel ligand- and silver-free palladium catalyst system for facile oxidative esterification of a variety of benzylic alcohols in good yields.

Comparison of photoenolization and alcohol release from alkyl-substituted benzoyl benzoic esters

Photolysis of 1B in argon-saturated solutions yields 4B and releases methanol. Laser flash photolysis of 1B shows formation of biradical 2B, which has a lifetime of ～50 ns and a max at 330 nm. Biradical 2B undergoes an intersystem crossing to form photoenols E-3B and Z-3B with a max at 390 nm. Laser flash photolysis shows that the lifetimes of E-3B and Z-3B are affected by the solvent. Density functional theory calculations demonstrate that the transition-state barrier for a 1,5-H atom shift from Z-3B to regenerate 1B is affected by the ortho-alkyl substituents, whereas the stereoelectronics of the alkyl substituent affect the transition-state barrier of E-3B as it undergoes electrocyclic ring closure to form 4B. The photoreactivity of 1B was compared with its analogous methyl and isopropyl derivatives 1A and 1C, respectively,to better estimate the effect of the alkyl substituent on reactivity.