Asymmetric synthesis of α,β-diamino acid derivatives with an aziridine-, azetidine- and γ-lactone-skeleton via Mannich-type additions across α-chloro-N-sulfinylimines.
The efficient asymmetric synthesis of new chiral γ-chloro-α,β-diamino acid derivatives via highly diastereoselective Mannich-type reactions of N-(diphenylmethylene) glycine esters across a chiral α-chloro-N-p-toluenesulfinylimine was developed. The influence of the base, LDA or LiHMDS, used for the formation of the glycine enolates, was of great importance for the anti-/syn-diastereoselectivity of the Mannich-type reaction. The γ-chloro-α,β-diamino acid derivatives proved to be excellent building blocks for ring closure towards optically pure anti- and syn-β,γ-aziridino-α-amino esters, and subsequent ring transformation into trans-3-aminoazetidine-2-carboxylic acid derivatives and α,β-diamino-γ-butyrolactones.
Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium.
Gert
G
Callebaut
Sven
S
Mangelinckx
Loránd
L
Kiss
Reijo
R
Sillanpää
Ferenc
F
Fülöp
Norbert
N
De Kimpe
D000596:Amino Acids / Q000737:chemistry*; D001384:Azetidines / Q000737:chemistry*; D001388:Aziridines / Q000737:chemistry*; D017606:Chlorine Compounds / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D007783:Lactones / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism; D013457:Sulfur Compounds / Q000737:chemistry*
D000596:Amino Acids; D001384:Azetidines; D001388:Aziridines; D017606:Chlorine Compounds; D007097:Imines; D007783:Lactones; D013457:Sulfur Compounds; C082735:azetidine; C033132:aziridine