Stereodivergent synthesis of chiral fullerenes by [3 + 2] cycloadditions to C60.
J Am Chem Soc
; 136(2): 705-12, 2014 Jan 15.
Article
en En
| MEDLINE
| ID: mdl-24359021
ABSTRACT
A wide range of new dipoles and catalysts have been used in 1,3-dipolar cycloadditions of N-metalated azomethine ylides onto C60 yielding a full stereodivergent synthesis of pyrrolidino[60]fullerenes with complete diastereoselectivities and very high enantioselectivities. The use of less-explored chiral α-iminoamides as starting 1,3-dipoles leads to an interesting double asymmetric induction resulting in a matching/mismatching effect depending upon the absolute configuration of the stereocenter in the starting α-iminoamide. An enantioselective process was also found in the retrocycloaddition reaction as revealed by mass spectrometry analysis on quasi-enantiomeric pyrrolidino[60]fullerenes. Theoretical DFT calculations are in very good agreement with the experimental data. On the basis of this agreement, a plausible reaction mechanism is proposed.
Texto completo:
1
Bases de datos:
MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
Año:
2014
Tipo del documento:
Article
País de afiliación:
España