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 Branchaud, Mark S. Meier

Research output: Contribution to journalArticle

47 Citations (Scopus)

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 languageEnglish (US)
Pages (from-to)1320-1326
Number of pages7
JournalJournal of Organic Chemistry
Volume54
Issue number6
DOIs
StatePublished - Mar 1 1989
Externally publishedYes

Fingerprint

Monosaccharides
Mannose
Ammonium Compounds
Keto Acids
Vanadium
Hydroxy Acids
Hydroxyl Radical
Ethanol
Carbohydrates
Derivatives
Oxidation
cobaloxime

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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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.",
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AU - Meier, Mark S.

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