Use of carbohydrate derivatives for studies of phosphorus stereochemistry. Part 8. Preparation and some reactions of 1,3,2-oxazaphospholidine-2-ones and -2-thiones derived from 2-deoxy-3,4,6-tri-O-methyl-2-methylamino-D-glucopyranose

C. Richard Hall, Thomas D. Inch, Colin Pottage, Nancy E. Williams, Malcolm M Campbell, Patrick F Kerr

Research output: Contribution to journalArticle

Abstract

The four cyclic phosphorus esters from the reaction of MePSCl2 with 2-deoxy-3,4,6-tri-O-methyl-2-methylamino-D-glucopyranose (1) have been separated with difficulty, and structures assigned. Ring-opening of the isomers and subsequent detachment of the chiral phosphorus group from the carbohydrate moiety occurs in both acid and base, the nature of the products varying with reaction conditions and initial stereochemistry. In acid the P-N bond is broken first and then the C-O bond. In base P-N and P-O bonds are cleaved competitively; when the P-N bond is cleaved first subsequent detachment of the phosphorus group from the carbohydrate occurs by C-O and P-O bond cleavage depending on the anomeric configuration and on the concentration of the base. The P-N and P-O bond breaking reactions are highly stereoselective occurring with inversion of configuration. Reactions of (1) with PhPSCl2, MePOCl2, and PhPOCl2 and ring-opening of the resultant esters are also described.

Original languageEnglish
Pages (from-to)1967-1975
Number of pages9
JournalJournal of the Chemical Society, Perkin Transactions 1
Publication statusPublished - 1983

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Thiones
Stereochemistry
Phosphorus
Carbohydrates
Derivatives
Esters
Acids
Isomers
(1,3,2)oxazaphospholidine

Cite this

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title = "Use of carbohydrate derivatives for studies of phosphorus stereochemistry. Part 8. Preparation and some reactions of 1,3,2-oxazaphospholidine-2-ones and -2-thiones derived from 2-deoxy-3,4,6-tri-O-methyl-2-methylamino-D-glucopyranose",
abstract = "The four cyclic phosphorus esters from the reaction of MePSCl2 with 2-deoxy-3,4,6-tri-O-methyl-2-methylamino-D-glucopyranose (1) have been separated with difficulty, and structures assigned. Ring-opening of the isomers and subsequent detachment of the chiral phosphorus group from the carbohydrate moiety occurs in both acid and base, the nature of the products varying with reaction conditions and initial stereochemistry. In acid the P-N bond is broken first and then the C-O bond. In base P-N and P-O bonds are cleaved competitively; when the P-N bond is cleaved first subsequent detachment of the phosphorus group from the carbohydrate occurs by C-O and P-O bond cleavage depending on the anomeric configuration and on the concentration of the base. The P-N and P-O bond breaking reactions are highly stereoselective occurring with inversion of configuration. Reactions of (1) with PhPSCl2, MePOCl2, and PhPOCl2 and ring-opening of the resultant esters are also described.",
author = "Hall, {C. Richard} and Inch, {Thomas D.} and Colin Pottage and Williams, {Nancy E.} and Campbell, {Malcolm M} and Kerr, {Patrick F}",
year = "1983",
language = "English",
pages = "1967--1975",
journal = "Journal of the Chemical Society, Perkin Transactions 1",
issn = "1472-7781",

}

TY - JOUR

T1 - Use of carbohydrate derivatives for studies of phosphorus stereochemistry. Part 8. Preparation and some reactions of 1,3,2-oxazaphospholidine-2-ones and -2-thiones derived from 2-deoxy-3,4,6-tri-O-methyl-2-methylamino-D-glucopyranose

AU - Hall, C. Richard

AU - Inch, Thomas D.

AU - Pottage, Colin

AU - Williams, Nancy E.

AU - Campbell, Malcolm M

AU - Kerr, Patrick F

PY - 1983

Y1 - 1983

N2 - The four cyclic phosphorus esters from the reaction of MePSCl2 with 2-deoxy-3,4,6-tri-O-methyl-2-methylamino-D-glucopyranose (1) have been separated with difficulty, and structures assigned. Ring-opening of the isomers and subsequent detachment of the chiral phosphorus group from the carbohydrate moiety occurs in both acid and base, the nature of the products varying with reaction conditions and initial stereochemistry. In acid the P-N bond is broken first and then the C-O bond. In base P-N and P-O bonds are cleaved competitively; when the P-N bond is cleaved first subsequent detachment of the phosphorus group from the carbohydrate occurs by C-O and P-O bond cleavage depending on the anomeric configuration and on the concentration of the base. The P-N and P-O bond breaking reactions are highly stereoselective occurring with inversion of configuration. Reactions of (1) with PhPSCl2, MePOCl2, and PhPOCl2 and ring-opening of the resultant esters are also described.

AB - The four cyclic phosphorus esters from the reaction of MePSCl2 with 2-deoxy-3,4,6-tri-O-methyl-2-methylamino-D-glucopyranose (1) have been separated with difficulty, and structures assigned. Ring-opening of the isomers and subsequent detachment of the chiral phosphorus group from the carbohydrate moiety occurs in both acid and base, the nature of the products varying with reaction conditions and initial stereochemistry. In acid the P-N bond is broken first and then the C-O bond. In base P-N and P-O bonds are cleaved competitively; when the P-N bond is cleaved first subsequent detachment of the phosphorus group from the carbohydrate occurs by C-O and P-O bond cleavage depending on the anomeric configuration and on the concentration of the base. The P-N and P-O bond breaking reactions are highly stereoselective occurring with inversion of configuration. Reactions of (1) with PhPSCl2, MePOCl2, and PhPOCl2 and ring-opening of the resultant esters are also described.

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M3 - Article

SP - 1967

EP - 1975

JO - Journal of the Chemical Society, Perkin Transactions 1

JF - Journal of the Chemical Society, Perkin Transactions 1

SN - 1472-7781

ER -