title: On the enhanced reactivity and selectivity of triazole formation in molecular flasks. A theoretical rationale.
abstract: The azide-alkyne cycloaddition assisted by a self-assembled molecular flask developed by Rebek and coworkers (Org. Lett., 2002, 4, 327) has been simulated by means of the ONIOM methodology, thereby evidencing the reliability of this theoretical approach to model such large encapsulated systems. Experimental evidences accounting for this transformation within the supramolecular assembly such as the significant rate enhancement, complete regioselectivity, and product inhibition as the reaction proceeds have been qualitatively disentangled through estimation of the energy barriers and the structural characteristics of the corresponding host-guest complexes.
authors.affiliation: Departamento de Química Orgánica e Inorgánica, QUOREX Research Group, Facultad de Ciencias, Universidad de Extremadura, E-06006 Badajoz, Spain. dcannie@unex.es
authors.forename: David
authors.initials: D
authors.lastname: Cantillo
authors.forename: Martín
authors.initials: M
authors.lastname: Ávalos
authors.forename: Reyes
authors.initials: R
authors.lastname: Babiano
authors.forename: Pedro
authors.initials: P
authors.lastname: Cintas
authors.forename: José L
authors.initials: JL
authors.lastname: Jiménez
authors.forename: Juan C
authors.initials: JC
authors.lastname: Palacios