Internal motions in a fulleropyrrolidine tertiary amide with axial chirality

Giuseppe Borsato; Federico Della Negra; Francesco Gasparrini; Domenico Misiti; Vittorio Lucchini; Giorgia Possamai; Claudio Villani; Alfonso Zambon

doi:10.1021/jo049485q

Internal motions in a fulleropyrrolidine tertiary amide with axial chirality

J Org Chem. 2004 Aug 20;69(17):5785-8. doi: 10.1021/jo049485q.

Authors

Giuseppe Borsato¹, Federico Della Negra, Francesco Gasparrini, Domenico Misiti, Vittorio Lucchini, Giorgia Possamai, Claudio Villani, Alfonso Zambon

Affiliation

¹ Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente Attive, Università di Roma "La Sapienza", P. le A. Moro 5, 00185 Roma, Italy.

PMID: 15307760
DOI: 10.1021/jo049485q

Abstract

The kinetic parameters for topomerization around the N-CO bond and enantiomerization around the C-CO bond in N-1-naphthoyl fulleropyrrolidine 1 and N-1-naphthoyl pyrrolidine 2 have been determined by dynamic NMR (line shape simulation and selective inversion transfer). The DeltaS(not =) values are negligible. The DeltaH# value for topomerization of 1 is smaller with respect to that of 2 by 4.3 kcal mol(-1) (explained by the electron-withdrawing effect of fullerene) and the value for enantiomerization is greater by 1.4 kcal mol(-1) (explained by the greater rigidity of the fulleropyrrolidine ring, as confirmed by ab initio analyses).