Artículo
Mechanistic insight into the acid-catalyzed isomerization of biomass-derived polysubstituted pyrrolidines: an experimental and DFT study
Gerosa, Gabriela Guillermina
; Grimblat, Nicolas
; Spanevello, Rolando Angel
; Suarez, Alejandra Graciela
; Sarotti, Ariel Marcelo
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Fecha de publicación:
01/2017
Editorial:
Royal Society of Chemistry
Revista:
Organic & Biomolecular Chemistry
ISSN:
1477-0520
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
The 1,3-dipolar cycloaddition reactions of azomethine ylides is one of the preferred methods for the synthesis of polysubstituted pyrrolidines. The use of chiral dipolarophiles derived from carbohydrates yields enantiomerically pure pyrrolidines, usually in good to excellent endo selectivities, along with other minor stereoisomers. Recently, we found an unusual isomerization event that allowed the isolation of useful pyrrolidines with relative stereochemistries difficult to obtain otherwise. Although a simple and efficient protocol to promote these transformations was developed, the mechanism was not fully unravelled. Herein, after a combination of experimental, spectroscopic and computational studies (using DFT methods) we propose that this isomerization event takes place through a retro-Mannich//Mannich cascade, via the formation of an iminium ion with E geometry.
Palabras clave:
Mechanistic
,
Isomerization
,
Biomass
,
Pyrrolidines
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Identificadores
Colecciones
Articulos(IQUIR)
Articulos de INST.DE QUIMICA ROSARIO
Articulos de INST.DE QUIMICA ROSARIO
Citación
Gerosa, Gabriela Guillermina; Grimblat, Nicolas; Spanevello, Rolando Angel; Suarez, Alejandra Graciela; Sarotti, Ariel Marcelo; Mechanistic insight into the acid-catalyzed isomerization of biomass-derived polysubstituted pyrrolidines: an experimental and DFT study; Royal Society of Chemistry; Organic & Biomolecular Chemistry; 15; 2; 1-2017; 426-434
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