Asymmetric synthesis of nitrogen-containing bioactive compounds via enantiopure sulfinimines

The object of the research in this thesis was to develop new methods for the asymmetric synthesis of amine derivatives using sulfinimines ( N-sulfinyl imines). One project involved an efficient method for the asymmetric synthesis of aziridine phosphonates via the aza-Darzen reaction. Addition of the anion of chloromethyl phosphonates to sulfinimines provided alpha-chloro beta-amino phosphonate intermediates, which on treatment with base cyclized to N-sulfinyl aziridine 2-phosphonates. Removal of the N-sulfinyl auxiliary to give NH aziridine was accomplished using MeMgBr. Ring opening of aziridine phosphonates under transfer hydrogenation conditions afforded enantiopure alpha- or beta-amino phosphonates, important amino acid surrogates.;Swern oxidation of NH aziridine 2-phosphonates provide 2H-azirine 3-phosphonates, a new class of chiral iminodienophiles which react with dimes to provide bicyclic and tricyclic amino phosphonates in excellent yield and stereoselectivity Hydrogenation of the bicyclic aziridine Diels-Alder adducts gave the first examples of enantiopure quaternary piperidine phosphonates.;Another project concerned N-sulfinyl delta-amino beta-ketophosphonates, a new sulfinimine derived chiral building block prepared by addition of the anion of dimethyl methyl phosphonate to N-sulfinyl beta-amino esters or to N-sulfinyl beta-amino Weinreb amides. Homer-Wadsworth-Emmons chemistry of N-sulfinyl delta-amino beta-ketophosphonates with aldehydes provided N-sulfinyl amino keto-2,7-dienes. These amino dimes undergo ring-closing metathesis with a Grubbs' catalyst to gave N-sulfinyl 4-aminocyclopentenones, which are key intermediates in the asymmetric synthesis of antiviral and anticancer carbocyclic nucleosides. (Abstract shortened by UMI.)...