Syntheses of non-aromatic medium and large rings synthesized via phenylnitrenium ions
| Autor: | Lilian Y. Watanabe, Paulo Marcos Donate, Joaquín M. Campos, Fernando Costa Archanjo, Gino Del Ponte |
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| Přispěvatelé: | [Del Ponte, Gino] Univ Sao Paulo, Fac Ciencias Farmaceut Ribeirao Preto, Dept Ciencias Farmaceut, Via Cafe S-N, BR-14040903 Ribeirao Preto, SP, Brazil, [Archanjo, Fernando C.] Univ Fed Vales Jequitinhonha & Mucuri, Fac Ciencias Biol & Saude, Dept Farm, Campus JK,Rodovia MGT 367,Km 583, BR-39100000 Diamantina, MG, Brazil, [Watanabe, Lilian Y.] Univ Sao Paulo, Fac Filosofia Ciencias & Letras Ribeirao Preto, Dept Quim, Ave Bandeirantes 3900, BR-14040901 Ribeirao Preto, SP, Brazil, [Donate, Paulo M.] Univ Sao Paulo, Fac Filosofia Ciencias & Letras Ribeirao Preto, Dept Quim, Ave Bandeirantes 3900, BR-14040901 Ribeirao Preto, SP, Brazil, [Campos, Joaquin M.] Fac Farm, Dept Quim Farmaceut & Organ, C Campus Cartuja S-N, Granada 18071, Spain, [Campos, Joaquin M.] Univ Granada, SAS, Inst Biosanitario Granada Ibs GRANADA, Granada, Spain, Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP), Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq), Coordenadoria de Aperfeicoamento de Pessoal de Nivel Superior (CAPES) |
| Jazyk: | angličtina |
| Rok vydání: | 2018 |
| Předmět: |
ÍONS
Medium rings Arylnitrenium ions Chemistry(all) Stereochemistry General Chemical Engineering Reactivities Nitroarenes 010402 general chemistry 01 natural sciences Medicinal chemistry Alkylnitrenium ions lcsh:Chemistry chemistry.chemical_compound Laser flash-photolysis Singlet-triplet gaps Nitrenium ions Remote intramolecular functionalization Trifluoroacetic acid Anilines Carboxylate Aryl azides Chloroform 010405 organic chemistry Regioselectivity Precursors General Chemistry Butene 0104 chemical sciences chemistry lcsh:QD1-999 Cyclization Yield (chemistry) Phenylnitrenium Chemical Engineering(all) Substitution Cyclooctadiene Methyl group Large rings |
| Zdroj: | Arabian Journal of Chemistry, Vol 11, Iss 3, Pp 415-425 (2018) Repositório Institucional da USP (Biblioteca Digital da Produção Intelectual) Universidade de São Paulo (USP) instacron:USP |
| ISSN: | 1878-5352 |
| Popis: | We describe the preparation of m-and p-substituted phenyl azides which, on treatment with trifluoromethanesulfonic acid in chloroform (and only in one case, after adding trifluoroacetic acid) at 0 degrees C, gives rise to the intermediate phenylnitrenium ions that undergo intramolecular cyclization to give six-, eight-membered carbocycles, and ten-membered heterocycles. Intramolecular cyclization of 1-(4-azidophenyl)-4-phenylbutane (3b) gives direct access to the 1,2,3,4-tetrahydronaphthalene lignan scaffold with a good yield. When the same reaction is carried out on 1-(3-azidophenyl)-4-phenylbutane (3a), the meta isomer of 3b, the 3-aminodibenzo[a, c] cyclooctadiene is obtained with a modest yield. When an ethoxycarbonyl group is introduced at position two of the butene chain [16a, as an E/Z mixture (1/4)], the ethyl 3-aminobenzo[a, c] octatriene carboxylate was the major compound, and the 10-membered heterocycle the minor one, both derived from (E)-16a. Finally, when a methyl group is located at the para position of the azido group [(E)1-6b], cyclization involves the carbon atom ortho to the nitrogen atom and the ethyl 4-methyl-1-tosylaminobenzo[ a, c] octatriene carboxylate is the only compound obtained, after treatment with tosyl chloride. With all these structural changes, we have switched over from the formation of mixtures of compounds to the regioselective formation of the target molecule, suggesting the corresponding mechanism of reaction and expanding the knowledge of this type of reaction. (C) 2016 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. |
| Databáze: | OpenAIRE |
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