A Novel Strategy for the Synthesis of Ammonium 3-Deoxy-D-manno-2-octulosonate (Ammonium KDO) from Lower Monosaccharides: C-C Bond Construction at C6of D-Mannose via Cobaloxime-Mediated Radical Alkyl-Alkenyl Cross Coupling

Bruce P. Branchaud; Mark S. Meier

doi:10.1021/jo00267a017

A Novel Strategy for the Synthesis of Ammonium 3-Deoxy-D-manno-2-octulosonate (Ammonium KDO) from Lower Monosaccharides: C-C Bond Construction at C₆of D-Mannose via Cobaloxime-Mediated Radical Alkyl-Alkenyl Cross Coupling

Bruce P. Branchaud, Mark S. Meier

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

53 Scopus citations

Abstract

Our synthesis of ammonium 3-deoxy-D-manno-2-octulosonate (ammonium KDO, 16) from D-mannose (3) proceeds in 10 one-flask operations in 1.5-1.6% overall yield (66% per operation). The strategic reaction is a C-C bond construction at C₆of D-mannose via photochemically induced radical cross coupling of a-ethoxyacrylonitrile with an alkyl cobaloxime derivative of D-mannose, in aqueous ethanol without protection of carbohydrate hydroxyls. In this paper we provide full experimental details of our KDO synthesis. In addition we provide some observations and insights on vanadium-catalyzed oxidations of a-hydroxy acids to a-keto acids.

Original language	English
Pages (from-to)	1320-1326
Number of pages	7
Journal	Journal of Organic Chemistry
Volume	54
Issue number	6
DOIs	https://doi.org/10.1021/jo00267a017
State	Published - Mar 1 1989

ASJC Scopus subject areas

Organic Chemistry

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@article{79f3fe4b59e24cf09aae26e96c25ba0d,

title = "A Novel Strategy for the Synthesis of Ammonium 3-Deoxy-D-manno-2-octulosonate (Ammonium KDO) from Lower Monosaccharides: C-C Bond Construction at C6of D-Mannose via Cobaloxime-Mediated Radical Alkyl-Alkenyl Cross Coupling",

abstract = "Our synthesis of ammonium 3-deoxy-D-manno-2-octulosonate (ammonium KDO, 16) from D-mannose (3) proceeds in 10 one-flask operations in 1.5-1.6% overall yield (66% per operation). The strategic reaction is a C-C bond construction at C6of D-mannose via photochemically induced radical cross coupling of a-ethoxyacrylonitrile with an alkyl cobaloxime derivative of D-mannose, in aqueous ethanol without protection of carbohydrate hydroxyls. In this paper we provide full experimental details of our KDO synthesis. In addition we provide some observations and insights on vanadium-catalyzed oxidations of a-hydroxy acids to a-keto acids.",

author = "Branchaud, {Bruce P.} and Meier, {Mark S.}",

year = "1989",

month = mar,

day = "1",

doi = "10.1021/jo00267a017",

language = "English",

volume = "54",

pages = "1320--1326",

number = "6",

}

A Novel Strategy for the Synthesis of Ammonium 3-Deoxy-D-manno-2-octulosonate (Ammonium KDO) from Lower Monosaccharides: C-C Bond Construction at C₆of D-Mannose via Cobaloxime-Mediated Radical Alkyl-Alkenyl Cross Coupling. / Branchaud, Bruce P.; Meier, Mark S.
In: Journal of Organic Chemistry, Vol. 54, No. 6, 01.03.1989, p. 1320-1326.

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

TY - JOUR

T1 - A Novel Strategy for the Synthesis of Ammonium 3-Deoxy-D-manno-2-octulosonate (Ammonium KDO) from Lower Monosaccharides

T2 - C-C Bond Construction at C6of D-Mannose via Cobaloxime-Mediated Radical Alkyl-Alkenyl Cross Coupling

AU - Branchaud, Bruce P.

AU - Meier, Mark S.

PY - 1989/3/1

Y1 - 1989/3/1

N2 - Our synthesis of ammonium 3-deoxy-D-manno-2-octulosonate (ammonium KDO, 16) from D-mannose (3) proceeds in 10 one-flask operations in 1.5-1.6% overall yield (66% per operation). The strategic reaction is a C-C bond construction at C6of D-mannose via photochemically induced radical cross coupling of a-ethoxyacrylonitrile with an alkyl cobaloxime derivative of D-mannose, in aqueous ethanol without protection of carbohydrate hydroxyls. In this paper we provide full experimental details of our KDO synthesis. In addition we provide some observations and insights on vanadium-catalyzed oxidations of a-hydroxy acids to a-keto acids.

AB - Our synthesis of ammonium 3-deoxy-D-manno-2-octulosonate (ammonium KDO, 16) from D-mannose (3) proceeds in 10 one-flask operations in 1.5-1.6% overall yield (66% per operation). The strategic reaction is a C-C bond construction at C6of D-mannose via photochemically induced radical cross coupling of a-ethoxyacrylonitrile with an alkyl cobaloxime derivative of D-mannose, in aqueous ethanol without protection of carbohydrate hydroxyls. In this paper we provide full experimental details of our KDO synthesis. In addition we provide some observations and insights on vanadium-catalyzed oxidations of a-hydroxy acids to a-keto acids.

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DO - 10.1021/jo00267a017

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JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 6

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