jo9623494_si_001.pdf (321.72 kB)
2,3-Aziridino-2,3-dideoxy-d-ribono-γ-lactone 5-Phosphonate: Stereocontrolled Synthesis from d-Lyxose and Unusual Aziridine Ring Opening
journal contribution
posted on 1997-06-27, 00:00 authored by Philippe Dauban, Robert H. DoddThe synthesis of
(1R,4S,5S)-N-(benzyloxycarbonyl)-4-[(diethoxyphosphinyl)methyl]-3-oxa-6-azabicyclo[3.1.0]hexan-2-one (23), a new member of the
2,3-aziridino γ-lactone family of compounds, was
achieved in 15 steps from d-lyxose. Like all aziridino
γ-lactones known so far, 23 reacted with a
soft nucleophile (ethanethiol) to give exclusively the product of
aziridine ring opening at C-2 (24).
On the other hand, hard nucleophiles (alcohols) did not react
directly with the aziridine ring of 23
but appeared to promote intramolecular attack of the aziridine ring at
C-3 by the C-5 phosphonate
group, resulting, after hydrolytic workup, in formation of the
2-amino-3-hydroxy-d-ribono-1,4-lactone
derivatives 25 and 26, instead of the expected
2-amino-3-alkoxy-d-xylono-1,4-lactone
derivatives.