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...
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Veröffentlicht in: | Acta crystallographica. Section E, Crystallographic communications Crystallographic communications, 2018-09, Vol.74 (9), p.1330-1335 |
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Hauptverfasser: | , , |
Format: | Artikel |
Sprache: | eng |
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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 . |
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ISSN: | 2056-9890 2056-9890 |
DOI: | 10.1107/S2056989018011349 |