40746-59-6

Upstream product

• 3319-15-1 rac-1-(4-methoxyphenyl)-ethanol 
• 4076-36-2 5-methyl-1,2,3,4-tetrazole 
• 100-66-3 methoxybenzene 
• 2475-92-5 (E)-1-(4-methoxyphenyl)ethanone oxime 
• 100-06-1 1-(4-methoxyphenyl)ethanone 
• 768-60-5 4-methoxyphenylacetylen 
• 5310-18-9 N-(4-methoxyphenyl)thioacetamide 

Downstream Products

• 1018238-53-3 2-[1-(4-methoxyphenyl)-1H-tetrazol-5-yl]acetic acid 
• 168267-03-6 2-methoxy-5-(5-methyl-tetrazol-1-yl)-benzaldehyde 

Relevant academic research and scientific papers

Dehydrative Beckmann rearrangement and the following cascade reactions

The Beckmann rearrangement has been predominantly studied for the synthesis of amide and lactam. By strategically using the in situ generated Appel's salt or Mitsunobu's zwitterionic adduct as the dehydrating agent, a series of Beckmann rearrangement and following cascade reactions have been developed herein. The protocol allows the conversion of various ketoximes into amide, thioamide, tetrazole and imide products in modular procedures. The generality and tolerance of functionalities of this method have been demonstrated.

Facile preparation of 5-alkyl-1-aryltetrazoles with arenes, acyl chlorides, hydroxylamine, and diphenylphosphoryl azide

Successive treatment of arenes with acyl chlorides and AlCl3, the addition of water and removal of solvent, the reaction with NH2OH?HCl and K2CO3, and the reaction with diphenylphosphoryl azide and DBU under warming conditions gave the corresponding 5-alkyl-1-aryltetrazoles efficiently in good to moderate yields. The present method is one-pot transformation of arenes into 5-alkyl-1-aryltetrazoles using the Friedel-Crafts acylation and the Beckmann rearrangement under transition-metal-free conditions.

Stereospecific synthesis of 1,5-disubstituted tetrazoles from ketoximes via a Beckmann rearrangement facilitated by diphenyl phosphorazidate

A novel method for the stereospecific synthesis of 1,5-disubstituted tetrazoles from ketoximes via the Beckmann rearrangement was developed using diphenyl phosphorazidate (DPPA) as both the oxime activator and azide source. Various ketoximes were transformed into the corresponding 1,5-disubstituted tetrazoles with exclusive trans-group migration and no E-Z isomerization of the ketoxime. This method enables the preparation of 1,5-disubstituted tetrazoles without using toxic or explosive azidation reagents.

Construction of 5-Aminotetrazoles via in Situ Generation of Carbodiimidium Ions from Ketones Promoted by TMSN3/TfOH

A novel synthetic approach for the synthesis of 5-aminotetrazoles has been developed by employing simple ketones as substrates. This methodology involved the N2-extrusion/aryl migration of azido complexes as the key step for the in situ generation of carbodiimidium ion, which could further react with hydrazoic acid and cyclize intramolecularly to provide 5-aminotetrazoles in good to excellent yields. In addition, the regioselectivity of the reaction was studied and rationalized by density functional theory calculations.

An efficient synthesis of nitrile, tetrazole and urea from carbonyl compounds

An efficient conversion of carbonyl compounds (aldehydes and ketones) to nitrile, tetrazole, and urea was developed with the use of a POCl3 and sodium azide mixture using a convergent and microwave method. This is the first report on the direct conversion of ketone to urea. The synthesized compounds were characterized by 1H NMR, 13C NMR, mass and IR spectroscopies and were found to be in agreement with reported compounds.

Copper-Catalyzed para-Selective C-H Amination of Electron-Rich Arenes

A one-pot two-step method for para-selective C-H amination of carbocyclic arenes comprises the in situ formation of unsymmetrical diaryl-λ3-iodanes followed by their Cu(I)-catalyzed reaction with a range of N-unprotected amines.

Site-selective arene C-H amination via photoredox catalysis

Over the past several decades, organometallic cross-coupling chemistry has developed into one of the most reliable approaches to assemble complex aromatic compounds from preoxidized starting materials. More recently, transition metal-catalyzed carbon-hydrogen activation has circumvented the need for preoxidized starting materials, but this approach is limited by a lack of practical amination protocols. Here, we present a blueprint for aromatic carbon-hydrogen functionalization via photoredox catalysis and describe the utility of this strategy for arene amination. An organic photoredox-based catalyst system, consisting of an acridinium photooxidant and a nitroxyl radical, promotes site-selective amination of a variety of simple and complex aromatics with heteroaromatic azoles of interest in pharmaceutical research. We also describe the atom-economical use of ammonia to form anilines, without the need for prefunctionalization of the aromatic component.

Copper-catalyzed oxidative transformation of secondary alcohols to 1,5-disubstituted tetrazoles

A mild and convenient oxidative transformation of secondary alcohols to 1,5-disubstituted tetrazoles is uncovered by employing trimethylsilyl azide (TMSN3) as a nitrogen source in the presence of a catalytic amount of copper(II) perchlorate hexahydrate [Cu(ClO4)2 .6 H2O] (5 mol%) and 2,3-dichloro-5,6-dicyano-para- benzoquinone (DDQ) (1.2 equiv.) as an oxidant. This reaction is performed under ambient conditions and proceeds through C-C bond cleavage.

Gold-catalyzed synthesis of tetrazoles from alkynes by Ci￡ C bond cleavage

Golden duality: Tetrazoles are formed by the reaction of alkynes with TMSN3 (TMS=trimethylsilyl) in the presence of iPrOH and the gold(I) catalyst [JohnPhosAu(MeCN)]SbF6. In this transformation gold plays a dual role, first activating the alkyne and then generating a Bronsted acid in situ.

Efficient uncatalyzed conversion of primary and secondary thioamides into 1-substituted, 5-substituted, 1, 5-disubstituted and annulated tetrazoles

Unprecedented high-yield simple and mild conversion of primary aliphatic and aromatic thioamides into 5-substituted tetrazoles on treatment with a combination of tetrachlorosilane and sodium azide in refluxing acetonitrile has been achieved. Secondary acyclic, cyclic, and heterocyclic thioamides could also be transformed in high yields into 1-substituted, 1,5-disubstituted, or annulated tetrazoles under the same reaction condition. Copyright Taylor & Francis Group, LLC.