53218-10-3

Upstream product

• 619-50-1 4-nitrobenzoic acid methyl ester 
• 15175-54-9 N,N-dimethyl-4-methoxylbenzylamine 
• 122-04-3 4-nitro-benzoyl chloride 
• 105-13-5 4-Methoxybenzyl alcohol 
• 62-23-7 4-nitro-benzoic acid 
• 25407-30-1 4-nitrophenacylpyridinium bromide 
• 99-81-0 4-Nitrophenacyl bromide 
• 555-16-8 4-nitrobenzaldehdye 
• 2746-25-0 p-Methoxybenzyl bromide 
• 100-11-8 1-bromomethyl-4-nitro-benzene 
• 123-11-5 4-methoxy-benzaldehyde 
• 121-98-2 methyl 4-methoxybenzoate 

Downstream Products

• 446867-23-8 4-methoxybenzyl 2,2,2-trifluoroethyl ether 
• 62-23-7 4-nitro-benzoic acid 
• 127866-65-3 5-[(4-methoxybenzyl)sulfanyl]-1-phenyl-1H-tetrazole 

Relevant academic research and scientific papers

Vitamin B1-catalyzed aerobic oxidative esterification of aromatic aldehydes with alcohols

A straightforward aerobic oxidative esterification of aryl aldehydes with alcohols has been developed for the synthesis of substituted esters by employing vitamin B1 as a cost-effective, metal-free, and eco-friendly NHC catalyst. Air is used as a green terminal oxidant. The reaction is a useful addition to the existing NHC-catalytic oxidative esterification.

N-Heterocyclic Carbene Catalyzed Ester Synthesis from Organic Halides through Incorporation of Oxygen Atoms from Air

Oxygenation reactions with molecular oxygen (O2) as the oxygen source provides a green and straightforward strategy for the construction of O-containing compounds. Demonstrated here is a novel N-heterocyclic carbene (NHC) catalyzed oxidative transformation of simple and readily available organic halides into valuable esters through the incorporation of O-atoms from O2. Mechanistic studies prove that the deoxy Breslow intermediate generated in situ is oxidized to a Breslow intermediate for further transformation by this oxidative protocol. This method broadens the field of NHC catalysis and promotes oxygenation reactions with O2.

A metal-free approach for the synthesis of amides/esters with pyridinium salts of phenacyl bromides via oxidative C–C bond cleavage

An efficient, simple, and metal-free synthetic approach for the N- and O-benzoylation of various amines/benzyl alcohols with pyridinium salts of phenacyl bromides is demonstrated to generate the corresponding amides and esters. This protocol facilitates the oxidative cleavage of a C–C bond followed by formation of a new C–N/C–O bond in the presence of K2CO3. Various pyridinium salts of phenacyl bromides can be readily transformed into a variety of amides and esters which is an alternative method for the conventional amidation and esterification in organic synthesis. High functional group tolerance, broad substrate scope and operational simplicity are the prominent advantages of the current protocol.

Mitsunobu Reactions Catalytic in Phosphine and a Fully Catalytic System

The Mitsunobu reaction is renowned for its mild reaction conditions and broad substrate tolerance, but has limited utility in process chemistry and industrial applications due to poor atom economy and the generation of stoichiometric phosphine oxide and hydrazine by-products that complicate purification. A catalytic Mitsunobu reaction using innocuous reagents to recycle these by-products would overcome both of these shortcomings. Herein we report a protocol that is catalytic in phosphine (1-phenylphospholane) employing phenylsilane to recycle the catalyst. Integration of this phosphine catalytic cycle with Taniguchi's azocarboxylate catalytic system provided the first fully catalytic Mitsunobu reaction. Make it catalytic: A catalytic Mitsunobu reaction using innocuous reagents to recycle the stoichiometric phosphine oxide and hydrazine by-products was developed. The reported method is catalytic in 1-phenylphospholane and uses phenylsilane to recycle the catalyst. Integration of this phosphine catalytic cycle with Taniguchi's azocarboxylate catalytic system provided the first fully catalytic Mitsunobu reaction.

Proton-exchanged montmorillonite-mediated reactions of methoxybenzyl esters and ethers

Proton-exchanged montmorillonite (H-mont) was found to be an eco-friendly and cost-effective catalyst for the generation of O-methylated quinone methides (QM) from the corresponding p or o-methoxybenzyl esters and ethers. Nucleophilic trapping of the O-methylated QM with arenes, alcohols, 1,3-dicarbonyl compounds, silyl enol ethers, and allylsilanes has been carried out, respectively, leading to eco-friendly benzylation reactions. Using this protocol, H-mont-mediated deprotection of PMB-protected esters and ethers have been realized for the first time. This work would pave the way for further exploration in O-alkylated QM that are of chemical and biological significance.

5,5′-Dimethyl-3,3′-azoisoxazole as a new heterogeneous azo reagent for esterification of phenols and selective esterification of benzylic alcohols under Mitsunobu conditions

5,5′-Dimethyl-3,3′-azoisoxazole is used as a new efficient heterogeneous azo reagent for the highly selective esterification of primary and secondary benzylic alcohols and phenols with aliphatic and aromatic carboxylic acids via Mitsunobu protocols. The reaction is highly selective for primary benzylic alcohols versus secondary ones, aliphatic alcohols and also phenols. The isoxazole hydrazine byproduct can be simply isolated by filtration and recycled to its azoisoxazole by oxidation.

Organocatalytic Mitsunobu reactions

A catalytic Mitsunobu reaction system is described in which the azo reagent is used as an organocatalyst and iodosobenzene diacetate is used as the stoichiometric oxidant. In this system, iodosobenzene diacetate oxidizes the formed hydrazine byproduct to regenerate the azo reagent. Yields obtained in the catalytic reactions using a variety of carboxylic acids and alcohols were slightly lower than those obtained from corresponding stoichiometric reactions. Both primary and secondary alcohols can be used as substrates in this reaction system, with the secondary alcohols affording products with inverted stereochemistry at the carbinol center. Copyright