Iodine(III)-Mediated Ring Contraction of 1,2-Dihydronaphthalenes: Mechanistic Insight by Computational Investigations

Autor(es)

Menezes da Silva, Vitor H. ; Silva, Jr., Luiz F. ; Braga, Ataualpa A. C.

• Tipo de documento: Artigo Científico
• Fonte: CHEMISTRYSELECT; v. 1, n. 11, p. 2706-2711, JUL 16 2016.
• Citações Web of Science: 2

Resumo

The metal-free synthesis of the trans-1,3-disubstituted indanes through the ring contraction of 1,2-dihydronaphtalenes, promoted by PhI(OH)Ts (HTIB or Koser's reagent), was computationally studied using Density Functional Theory (DFT) methods. DFT calculations suggest that the stereoselectivity of these reactions arises through the torsional effects during the electro-philic addition of the hypervalent iodine to the double bond of the 1,2-dihydronaphthalene. Furthermore, the fundamental role played by the solvent (MeOH) during the nucleophilic addition step was analyzed by DFT methods on a mixed continuum-microsolvation model system. (AU)

• Processo FAPESP: 13/04813-6 - Estudos mecanísticos da reação de Heck-Matsuda: uma investigação teórica
• Beneficiário: Vitor Hugo Menezes da Silva
• Modalidade de apoio: Bolsas no Brasil - Doutorado
• Processo FAPESP: 15/01491-3 - Estudo teórico das reações de acoplamento-cruzado: catálise homogênea e heterogênea
• Beneficiário: Ataualpa Albert Carmo Braga
• Modalidade de apoio: Auxílio à Pesquisa - Regular