Palladium-Mediated Catalysis Leads to Intramolecular Narcissistic Self-Sorting on a Cavitand Platform

Author(s)

Nagymihaly, Zoltan ; Caturello, Naidel A. M. S. ; Takatsy, Aniko ; Aragay, Gemma ; Kollar, Laszlo ; Albuquerque, Rodrigo Q. ; Csok, Zsolt

• Document type: Journal article
• Source: Journal of Organic Chemistry; v. 82, n. 1, p. 390-396, JAN 6 2017.
• Web of Science Citations: 2

Abstract

Palladium-catalyzed aminocarbonylation reactions have been used to directly convert a tetraiodocavitand intermediate into the corresponding carboxamides and 2-ketocarboxamides. When complex mixtures of the amine reactants are employed in competition experiments using polar solvents, such as DMF, no ``mixed{''} products possessing structurally different amide fragments are detected either by H-1 or C-13 NMR Only highly symmetrical cavitands are sorted out of a large number of potentially feasible products, which represents a rare example of intramolecular, narcissistic self-sorting. Our experimental results along with thermodynamic energy analysis suggest that the observed self-sorting is a symmetry-driven, kinetically controlled process. (AU)

• FAPESP's process: 14/02071-5 - Theoretical investigation of the aggregation of cationic complexes of Ir(III) with potential application in LECs and OLEDs
• Grantee: Rodrigo Queiroz de Albuquerque
• Support type: Regular Research Grants