38446-87-6Relevant academic research and scientific papers
Bu4NI-Catalyzed, Radical-Induced Regioselective N-Alkylations and Arylations of Tetrazoles Using Organic Peroxides/Peresters
Ghosh, Subhendu,Mir, Bilal Ahmad,Patel, Bhisma K.,Rajamanickam, Suresh,Sah, Chitranjan,Sethi, Garima,Venkataramani, Sugumar,Yadav, Vinita
, p. 2118 - 2141 (2020/03/13)
Bu4NI-catalyzed regioselective N2-methylation, N2-Alkylation, and N2-Arylation of tetrazoles have been achieved using tert-butyl hydroperoxide (TBHP) as the methyl source, alkyl diacyl peroxides as the primary alkyl source, alkyl peresters as the secondary and tertiary alkyl sources, and aryl diacyl peroxides as the arylating source. These reactions proceed without pre-functionalization of tetrazole and in the absence of any metal catalysts. Here, peroxides serve the dual role of oxidants as well as alkylating or arylating agents. Based on DFT calculations, it was found that spin density, transition-state barriers (kinetic control), and thermodynamic stability of the products (thermodynamic control) play essential roles in the observed regioselectivity during N-Alkylation. This radical-mediated process is amenable to a broad range of substrates and provides products in moderate to good yields.
Palladium-Catalyzed Methylation of Aryl, Heteroaryl, and Vinyl Boronate Esters
Haydl, Alexander M.,Hartwig, John F.
supporting information, p. 1337 - 1341 (2019/02/26)
A method for the direct methylation of aryl, heteroaryl, and vinyl boronate esters is reported, involving the reaction of iodomethane with aryl-, heteroaryl-, and vinylboronate esters catalyzed by palladium and PtBu2Me. This transformation occurs with a remarkably broad scope and is suitable for late-stage derivatization of biologically active compounds via the boronate esters. The unique capabilities of this method are demonstrated by combining carbon-boron bond-forming reactions with palladium-catalyzed methylation in a tandem transformation.
Preparation of 5-Aryl-2-Alkyltetrazoles with Aromatic Aldehydes, Alkylhydrazine, Di-tert-butyl Azodicarboxylate, and [Bis(trifluoroacetoxy)iodo]benzene
Imai, Taro,Harigae, Ryo,Moriyama, Katsuhiko,Togo, Hideo
, p. 3975 - 3980 (2016/05/24)
A variety of 5-aryl-2-methyltetrazoles and 5-aryl-2-benzyltetrazoles were directly prepared in good to moderate yields by the reaction of aromatic aldehydes with methylhydrazine and benzylhydrazine, followed by treatment with di-tert-butyl azodicarboxylate and [bis(trifluoroacetoxy)iodo]benzene in a mixture of dichloromethane and 2,2,2-trifluoroethanol at room temperature. The present method is a novel one-pot preparation of 5-aryl-2-methyltetrazoles and 5-aryl-2-benzyltetrazoles through a [2N + 2N] combination under transition metal-free and mild conditions.
Rhodium-catalyzed olefination of aryl tetrazoles via direct C-H bond activation
Wang, Liang,Wu, Wenting,Chen, Qun,He, Mingyang
, p. 7923 - 7926 (2015/01/09)
Rh(III)-catalyzed direct olefination reaction via aromatic C-H bond activation is described using tetrazole as the directing group. This reaction provides a straightforward way for the synthesis of ortho-alkenyl aryl tetrazoles. Various functional groups tolerate the reaction conditions and afford the corresponding products in moderate to excellent yields.
TETRAZOLES. XVI. ALKYLATION OF TETRAZOLES UNDER THE CONDITIONS OF PHASE-TRANSFER CATALYSIS
Osipova, T. F.,Ostrovskii, V. A.,Koldobskii, G. I.,Erusalimskii, G. B.
, p. 357 - 362 (2007/10/02)
The alkylation of tetrazole and 5-substituted tetrazoles with dimethyl sulfate and methyl iodide in the two-phase methylene chloride-water system in the presence of tetrabutylammonium bromide was investigated.The alkylation of tetrazoles with methyl iodide takes place in the organic phase, while that with dimethyl sulfate takes place both in the organic and in the aqueous phases.The ratio of the isomeric tetrazoles formed during the alkylation of 5-aryltetrazoles by methyl iodide correlate with the substituent constants ?.The use of phase-transfer catalysis during the alkylation of tetrazoles does not lead to a change in the selectivity of the reaction.
TETRAZOLES. VIII. KINETICS AND RATIO OF THE REACTION PRODUCTS IN THE ALKYLATION OF THE SALTS OF SUBSTITUTED 5-PHENYLTETRAZOLES BY DIMETHYL SULFATE IN ACETONITRILE
Ostrovskii, V. A.,Shirobokov, I. Yu.,Koldobskii, G. I.
, p. 131 - 135 (2007/10/02)
The kinetics and the ratio of the reaction products were investigated for the alkylation of potassium salts of a series of substituted 5-phenyltetrazoles by dimethyl sulfate in acetonitrile.It was shown that with the salt at a concentration of less than 10-3M the corresponding tetrazolate ion enters into reaction with dimethyl sulfate.Electron-withdrawing substituents in the benzene ring reduce the rate of the alkylation reaction and help to increase the proportion of the N2 isomer in the reaction products.The rate constants for the reaction of substituted 5-phenyltetrazoles with dimethyl sulfate and the ratios of the isomeric tetrazoles formed during alkylation correlate with the ? constants of the substituents.
A Study of Annular Tautomerism, Interannular Conjugation, and Methylation Reactions of ortho-Substituted-5-aryltetrazoles using Carbon-13 and Hydrogen-1 N.M.R. Spectroscopy
Butler, Richard N.,Garvin, Victor C.
, p. 390 - 393 (2007/10/02)
In ortho-substituted-5-phenyltetrazoles, Ar-CN4H (Ar = 2'-MeC6H4, 2'-ClC6H4, or 2',6'-Cl2C6H3), the rings are twisted out of the planar configuration and interannular conjugation is inhibited.In each case the tetrazole 1-NH tautomer is strongly predominan
