The stereoselective addition of aryl and alkylacetylene derivatives to immines was the first reaction studied. The reaction is catalyzed by copper complexes of enantiomerically pure bisimines prepared in very high yields from the commercially available binaphthyldiamine. A simple experimental procedure allowed to obtain at room temperature optically active propargylamines in high yields and enantioselectivities up to 85%. A three-component stereoselective reaction between an aldehyde, an amine and phenylacetylene to afford active propargyl amines in good yields and enantioselectivities up to 75% was also developed. The stereoselective addition of phenyl acetylene to imines, catalysed by chiral bis-amine-Cu (I) complexes was also studied. The chiral ligands are either commercially available or easily prepared in one or two steps. This convenient and simple experimental procedure at room temperature allowed to obtain optically active propargyl amines in good yields and enantioselectivities up to 70%. The catalytic enantioselective addition of allyltributylstannane to N-protected a-iminoesters promotedby silver (I) trifluoromethanesulfonate in the presence of chiral imine ligands wsa the second reaction studied during PhD. After testing several chiral imines derive from 1,2-diaminocyclohexane and binaphthyl diamine a very simple experimental procedure was developed that allowed us to obtain optically active homoallylic amines in high yields and enantioselectivities up to 71%.
|Titolo:||Nuovi sistemi catalitici per l'addizione stereoselettiva di nulceofili ad immine|
|Autori interni:||COLOMBO, FEDERICA|
|Supervisori e coordinatori interni:||COZZI, FRANCO|
|Data di pubblicazione:||2007|
|Settore Scientifico Disciplinare:||Settore CHIM/06 - Chimica Organica|
|Citazione:||Nuovi sistemi catalitici per l'addizione stereoselettiva di nulceofili ad immine ; F. Cozzi. - Milano : Università degli studi di Milano. DIPARTIMENTO DI CHIMICA ORGANICA E INDUSTRIALE, 2007. ((20. ciclo, Anno Accademico 2006/2007.|
|Appare nelle tipologie:||13 - Tesi di dottorato discussa entro ottobre 2010|