150737-46-5Relevant articles and documents
Stereoselective synthesis of polyhydroxylated pyrrolidines: a route to novel 3,5-bis(hydroxymethyl)pyrrolidines from 2-azabicyclo[2.2.1]hept-5-enes
Alves, M. José,García-Mera, Xerardo,Vale, M. Luisa C.,Santos, Teresa P.,Aguiar, Fábio R.,Rodríguez-Borges, José E.
, p. 7595 - 7597 (2006)
An efficient preparation of racemic and chiral 2-functionalized-3,5-bis(hydroxymethyl)pyrrolidines is described. The method uses 2-azabicyclo[2.2.1]hept-5-enes, readily obtained from glyoxylates of aliphatic amines and cyclopentadiene, as starting material. The hydroxylation of the double bond followed by the oxidative cleavage of the six-membered ring and in situ reduction of the dialdehyde intermediate gives the title pyrrolidines.
Experimental and DFT study of the aza-Diels-Alder reaction between cyclopentadiene and protonated benzylimine derivated from glyoxylates
Rodríguez-Borges, José Enrique,García-Mera, Xerardo,Fernández, Franco,Lopes, V. Hugo C.,Magalh?es,Cordeiro, M. Natália D. S.
, p. 10951 - 10957 (2007/10/03)
The Diels-Alder reaction of protonated N-benzyl imine of methyl glyoxylate with cyclopentadiene in different solvents gave mixtures of exo/endo adducts. The exo/endo selectivity of the reaction was elucidated by NMR experiments. Theoretical calculations by means of density functional theory (DFT) at the B3LYP/6-31G(d) level have also been performed to elucidate the molecular mechanism of this reaction. The DFT results suggest a highly asynchronous concerted mechanism, which in turn can explain the preferred exo stereoselectivity of the reaction. Inclusion of solvent effects enhances the exo selectivity, and this effect increases with the polarity of the solvent, in good agreement with the experimental findings.
