Unexpected reactions of (1R)2,3,4,6-tetra-O-acetyl-1-azido-D-galactopyranosyl cyanide and the derived carboxamide with triphenylphosphine

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Abstract

Staudinger reaction of acetylated (1R)-1-azido-D-galactopyranosyl cyanide (1) with triphenylphosphine in diethyl ether led to the isolation of a crystalline phosphazide (2), unprecedented in carbohydrate chemistry. Spontaneous decomposition of 2 in toluene furnished the mixture of the unsaturated lactone 4, as minor product, and two major products: the triphenylphosphoranylidene derivatives of (2Z,4Z)-3-cyano-4,6-diacetoxy-2,4-hexadienoic amide (5), and (2E,4Z)-triacetoxy-2,4-hexadienoic amide (6), respectively, owing to an unusual pyranoid ring opening between C-5 and the pyranose oxygen. The carboxamide analogue (10) of 1 underwent a regular phosphinimine formation affording the equilibrium mixture of both anomers 11 and 12.

Original languageEnglish
Pages (from-to)15041-15050
Number of pages10
JournalTetrahedron
Volume53
Issue number44
DOIs
Publication statusPublished - nov. 3 1997

Fingerprint

Cyanides
Amides
Toluene
Lactones
Ether
Carbohydrates
Oxygen
Crystalline materials
Derivatives
Decomposition
triphenylphosphine
3'-azido-2',3'-dideoxythymidine 5'-H-phoshonate

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

@article{6f6cc625d62c45c28c2049bd3019038d,
title = "Unexpected reactions of (1R)2,3,4,6-tetra-O-acetyl-1-azido-D-galactopyranosyl cyanide and the derived carboxamide with triphenylphosphine",
abstract = "Staudinger reaction of acetylated (1R)-1-azido-D-galactopyranosyl cyanide (1) with triphenylphosphine in diethyl ether led to the isolation of a crystalline phosphazide (2), unprecedented in carbohydrate chemistry. Spontaneous decomposition of 2 in toluene furnished the mixture of the unsaturated lactone 4, as minor product, and two major products: the triphenylphosphoranylidene derivatives of (2Z,4Z)-3-cyano-4,6-diacetoxy-2,4-hexadienoic amide (5), and (2E,4Z)-triacetoxy-2,4-hexadienoic amide (6), respectively, owing to an unusual pyranoid ring opening between C-5 and the pyranose oxygen. The carboxamide analogue (10) of 1 underwent a regular phosphinimine formation affording the equilibrium mixture of both anomers 11 and 12.",
author = "J. Kov{\'a}cs and I. Pint{\'e}r and M. Kajt{\'a}r-Peredy and L. Soms{\'a}k",
year = "1997",
month = "11",
day = "3",
doi = "10.1016/S0040-4020(97)01055-7",
language = "English",
volume = "53",
pages = "15041--15050",
journal = "Tetrahedron",
issn = "0040-4020",
publisher = "Elsevier Limited",
number = "44",

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TY - JOUR

T1 - Unexpected reactions of (1R)2,3,4,6-tetra-O-acetyl-1-azido-D-galactopyranosyl cyanide and the derived carboxamide with triphenylphosphine

AU - Kovács, J.

AU - Pintér, I.

AU - Kajtár-Peredy, M.

AU - Somsák, L.

PY - 1997/11/3

Y1 - 1997/11/3

N2 - Staudinger reaction of acetylated (1R)-1-azido-D-galactopyranosyl cyanide (1) with triphenylphosphine in diethyl ether led to the isolation of a crystalline phosphazide (2), unprecedented in carbohydrate chemistry. Spontaneous decomposition of 2 in toluene furnished the mixture of the unsaturated lactone 4, as minor product, and two major products: the triphenylphosphoranylidene derivatives of (2Z,4Z)-3-cyano-4,6-diacetoxy-2,4-hexadienoic amide (5), and (2E,4Z)-triacetoxy-2,4-hexadienoic amide (6), respectively, owing to an unusual pyranoid ring opening between C-5 and the pyranose oxygen. The carboxamide analogue (10) of 1 underwent a regular phosphinimine formation affording the equilibrium mixture of both anomers 11 and 12.

AB - Staudinger reaction of acetylated (1R)-1-azido-D-galactopyranosyl cyanide (1) with triphenylphosphine in diethyl ether led to the isolation of a crystalline phosphazide (2), unprecedented in carbohydrate chemistry. Spontaneous decomposition of 2 in toluene furnished the mixture of the unsaturated lactone 4, as minor product, and two major products: the triphenylphosphoranylidene derivatives of (2Z,4Z)-3-cyano-4,6-diacetoxy-2,4-hexadienoic amide (5), and (2E,4Z)-triacetoxy-2,4-hexadienoic amide (6), respectively, owing to an unusual pyranoid ring opening between C-5 and the pyranose oxygen. The carboxamide analogue (10) of 1 underwent a regular phosphinimine formation affording the equilibrium mixture of both anomers 11 and 12.

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U2 - 10.1016/S0040-4020(97)01055-7

DO - 10.1016/S0040-4020(97)01055-7

M3 - Article

AN - SCOPUS:0342617529

VL - 53

SP - 15041

EP - 15050

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 44

ER -