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

Author(s)

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

• Document type: Journal article
• Source: CHEMISTRYSELECT; v. 1, n. 11, p. 2706-2711, JUL 16 2016.
• Web of Science Citations: 2

Abstract

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)

• FAPESP's process: 13/04813-6 - Mechanistic studies of Heck-Matsuda reactions: a theoretical investigation
• Grantee: Vitor Hugo Menezes da Silva
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 15/01491-3 - Theoretical study of cross-coupling reactions: homogeneous and heterogeneous catalysis
• Grantee: Ataualpa Albert Carmo Braga
• Support Opportunities: Regular Research Grants