Crystal structures of chiral 2-[bis(2-chloroethyl)amino]-1,3,2-oxazaphospholidin-2-one derivatives for the absolute configuration at phosphorus

`Nitrogen mustard' bis(2-chloroethyl)amine derivatives (2 R ,4 S ,5 R )- and (2 S ,4 S ,5 R )-2-[bis(2-chloroethyl)amino]-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one ( 2a and 2b , respectively), C 14 H 21 Cl 2 N 2 O 2 P, and (2 R ,4 R )- and (2 S ,4 R )-2-[bis(2-chloroethyl)amino]-4-iso...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Acta crystallographica. Section E, Crystallographic communications Crystallographic communications, 2018-09, Vol.74 (9), p.1330-1335
Hauptverfasser: Rohde Jr, Laurence N., Zeller, Matthias, Jackson, John A.
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:`Nitrogen mustard' bis(2-chloroethyl)amine derivatives (2 R ,4 S ,5 R )- and (2 S ,4 S ,5 R )-2-[bis(2-chloroethyl)amino]-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one ( 2a and 2b , respectively), C 14 H 21 Cl 2 N 2 O 2 P, and (2 R ,4 R )- and (2 S ,4 R )-2-[bis(2-chloroethyl)amino]-4-isobutyl-1,3,2-oxazaphospholidin-2-one ( 3a and 3b , respectively), C 10 H 21 Cl 2 N 2 O 2 P, were synthesized as a mixture of diastereomers through a 1:1 reaction of enantiomerically pure chiral amino alcohols with bis(2-chloroethyl)phosphoramidic dichloride. Flash column chromatography yielded diastereomerically pure products, as supported by 31 P NMR. The crystal structures of 2b and 3b were obtained to determine their absolute configuration at phosphorus, and 31 P NMR chemical shift trends are proposed based on the spatial relationship of the bis(2-chloroethyl)amine moiety and the chiral substituent of the amino alcohol. Oxazaphospholidinones were observed to have a more downfield 31 P NMR chemical shift when the aforementioned substituents are in a syn configuration and vice versa for when they are anti .
ISSN:2056-9890
2056-9890
DOI:10.1107/S2056989018011349