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 language | English |
|---|---|
| Pages (from-to) | 1967-1975 |
| Number of pages | 9 |
| Journal | Journal of the Chemical Society, Perkin Transactions 1 |
| Publication status | Published - 1983 |
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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. / Hall, C. Richard; Inch, Thomas D.; Pottage, Colin; Williams, Nancy E.; Campbell, Malcolm M; Kerr, Patrick F.
In: Journal of the Chemical Society, Perkin Transactions 1, 1983, p. 1967-1975.Research output: Contribution to journal › Article
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.
UR - http://www.scopus.com/inward/record.url?scp=37049107712&partnerID=8YFLogxK
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 -