A New Route for Preparation of 5-Deoxy-5-(hydroxyphosphinyl)- D-mannopyranose and -L-gulopyranose Derivatives

Starting from methyl 2,3-O-isopropylidene-α-D-mannofuranoside (5), methyl 6-O-benzyl-2,3-O-isopropylidene-α-D-lyxo-hexofuranosid-5-ulose (12) was prepared in three steps. The addition reaction of dimethyl phosphonate to 12, followed by deoxygenation of 5-OH group, provided the 5-deoxy-5-dimethoxyphosphinyl-α-D-mannofuranoside derivative 15a and the β-L-gulofuranoside isomer 15b. Reduction of 15a and 15b with sodium dihydrobis(2-methoxyethoxy)aluminate, followed by the action of HCl and then H2O2, afforded the D-mannopyranose (17) and L-gulopyranose analog 21, each having a phosphinyl group in the hemiacetal ring. These were converted to the corresponding 1,2,3,4,6-penta-O-acetyl-5-methoxyphosphinyl derivatives 19 and 23, respectively, structures and conformations (4C1 or 1C4, resp.) of which were established by 1H-NMR spectroscopy.

This is the peer reviewed version of the following article: Hanaya, T. and Yamamoto, H. (2002), A New Route for Preparation of 5-Deoxy-5-(hydroxyphosphinyl)- D-mannopyranose and -L-gulopyranose Derivatives. HCA, 85: 2608-2618. https://doi.org/10.1002/1522-2675(200209)85:9<2608::AID-HLCA2608>3.0.CO;2-F, which has been published in final form at https://doi.org/10.1002/1522-2675(200209)85:9<2608::AID-HLCA2608>3.0.CO;2-F. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.