Alkoxyl radical fragmentation of 3-azido-2,3-dideoxy-2-halo-hexopyranoses: a new entry to chiral polyhydroxylated 2-azido-1-halo-1-alkenes

Carmen R. Alonso-Cruz; Alan R. Kennedy; Maria S. Rodriguez; Ernesto Suarez

doi:10.1016/j.tetlet.2007.07.190

Alkoxyl radical fragmentation of 3-azido-2,3-dideoxy-2-halo-hexopyranoses: a new entry to chiral polyhydroxylated 2-azido-1-halo-1-alkenes

Carmen R. Alonso-Cruz, Alan R. Kennedy, Maria S. Rodriguez, Ernesto Suarez

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

23 Citations (Scopus)

Abstract

A new general two-step methodology for the synthesis of chiral fluoro, chloro, bromo and iodo vinyl azides from carbohydrate-derived halohydrins has been developed. The anomeric alkoxyl radical fragmentation of 3-azido-2,3-dideoxy-2-halo-pyranoses under oxidative conditions with (diacetoxyiodo) benzene and iodine gave 2-azido-1,2-dideoxy-1-halo-1-iodo-alditols, which by chemoselective dehydroiodination afforded (Z, E)-2-azido-1,2-dideoxy-1-halo-4-O-formyl-pent-1-enitols in good overall yields. Preliminary thermolysis and photochemical studies of these compounds for the synthesis of hitherto unknown disubstituted 2-halo-3-alkyl-2H-azirines have also been accomplished. (C) 2007 Elsevier Ltd. All rights reserved.

Original language	English
Pages (from-to)	7207-7210
Number of pages	4
Journal	Tetrahedron Letters
Volume	48
Issue number	40
DOIs	https://doi.org/10.1016/j.tetlet.2007.07.190
Publication status	Published - 1 Oct 2007

Keywords

x-ray structure
vinyl azides
olefins
facile synthesis
stereochemistry
isomerization
heterocycles

Access to Document

10.1016/j.tetlet.2007.07.190

x-ray diffractometer
Kennedy, A.
Pure And Applied Chemistry
Facility/equipment: Equipment

Cite this

@article{290f4b1cc2104ac0af4489cc81f59a14,

title = "Alkoxyl radical fragmentation of 3-azido-2,3-dideoxy-2-halo-hexopyranoses: a new entry to chiral polyhydroxylated 2-azido-1-halo-1-alkenes",

abstract = "A new general two-step methodology for the synthesis of chiral fluoro, chloro, bromo and iodo vinyl azides from carbohydrate-derived halohydrins has been developed. The anomeric alkoxyl radical fragmentation of 3-azido-2,3-dideoxy-2-halo-pyranoses under oxidative conditions with (diacetoxyiodo) benzene and iodine gave 2-azido-1,2-dideoxy-1-halo-1-iodo-alditols, which by chemoselective dehydroiodination afforded (Z, E)-2-azido-1,2-dideoxy-1-halo-4-O-formyl-pent-1-enitols in good overall yields. Preliminary thermolysis and photochemical studies of these compounds for the synthesis of hitherto unknown disubstituted 2-halo-3-alkyl-2H-azirines have also been accomplished. (C) 2007 Elsevier Ltd. All rights reserved.",

keywords = "x-ray structure, vinyl azides, olefins, facile synthesis, stereochemistry, isomerization, heterocycles",

author = "Alonso-Cruz, {Carmen R.} and Kennedy, {Alan R.} and Rodriguez, {Maria S.} and Ernesto Suarez",

year = "2007",

month = oct,

day = "1",

doi = "10.1016/j.tetlet.2007.07.190",

language = "English",

volume = "48",

pages = "7207--7210",

journal = "Tetrahedron Letters",

issn = "0040-4039",

publisher = "Elsevier Limited",

number = "40",

}

TY - JOUR

T1 - Alkoxyl radical fragmentation of 3-azido-2,3-dideoxy-2-halo-hexopyranoses: a new entry to chiral polyhydroxylated 2-azido-1-halo-1-alkenes

AU - Alonso-Cruz, Carmen R.

AU - Kennedy, Alan R.

AU - Rodriguez, Maria S.

AU - Suarez, Ernesto

PY - 2007/10/1

Y1 - 2007/10/1

N2 - A new general two-step methodology for the synthesis of chiral fluoro, chloro, bromo and iodo vinyl azides from carbohydrate-derived halohydrins has been developed. The anomeric alkoxyl radical fragmentation of 3-azido-2,3-dideoxy-2-halo-pyranoses under oxidative conditions with (diacetoxyiodo) benzene and iodine gave 2-azido-1,2-dideoxy-1-halo-1-iodo-alditols, which by chemoselective dehydroiodination afforded (Z, E)-2-azido-1,2-dideoxy-1-halo-4-O-formyl-pent-1-enitols in good overall yields. Preliminary thermolysis and photochemical studies of these compounds for the synthesis of hitherto unknown disubstituted 2-halo-3-alkyl-2H-azirines have also been accomplished. (C) 2007 Elsevier Ltd. All rights reserved.

AB - A new general two-step methodology for the synthesis of chiral fluoro, chloro, bromo and iodo vinyl azides from carbohydrate-derived halohydrins has been developed. The anomeric alkoxyl radical fragmentation of 3-azido-2,3-dideoxy-2-halo-pyranoses under oxidative conditions with (diacetoxyiodo) benzene and iodine gave 2-azido-1,2-dideoxy-1-halo-1-iodo-alditols, which by chemoselective dehydroiodination afforded (Z, E)-2-azido-1,2-dideoxy-1-halo-4-O-formyl-pent-1-enitols in good overall yields. Preliminary thermolysis and photochemical studies of these compounds for the synthesis of hitherto unknown disubstituted 2-halo-3-alkyl-2H-azirines have also been accomplished. (C) 2007 Elsevier Ltd. All rights reserved.

KW - x-ray structure

KW - vinyl azides

KW - olefins

KW - facile synthesis

KW - stereochemistry

KW - isomerization

KW - heterocycles

U2 - 10.1016/j.tetlet.2007.07.190

DO - 10.1016/j.tetlet.2007.07.190

M3 - Article

SN - 0040-4039

VL - 48

SP - 7207

EP - 7210

JO - Tetrahedron Letters

JF - Tetrahedron Letters

IS - 40

ER -

Alkoxyl radical fragmentation of 3-azido-2,3-dideoxy-2-halo-hexopyranoses: a new entry to chiral polyhydroxylated 2-azido-1-halo-1-alkenes

Abstract

Keywords

Access to Document

Fingerprint

Equipment

x-ray diffractometer

Cite this