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Stereodivergent synthesis of jaspine B and its isomers using a carbohydrate-derived alkoxyallene as C3-building block.

ABSTRACT: Herein we present the synthesis of the anhydrophytosphingosine jaspine B and three of its stereoisomers using a carbohydrate-derived alkoxyallene in order to obtain the products in enantiopure form. Key step of the reaction sequence is the addition of the lithiated alkoxyallene to pentadecanal, setting the configuration at the later C-2 of the ring system. This reaction step proceeds with moderate selectivity and therefore leads to a stereodivergent approach to the natural product and its enantiomer. The gold-catalyzed 5-endo-cyclization affords the corresponding dihydrofurans, which after separation, azidation of the enol ether moiety and two subsequent reduction steps give the natural product and its stereoisomers.

SUBMITTER: Schmiedel VM

PROVIDER: S-EPMC3869275 | biostudies-literature | 2013

REPOSITORIES: biostudies-literature

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Stereodivergent synthesis of jaspine B and its isomers using a carbohydrate-derived alkoxyallene as C3-building block.

Schmiedel Volker Martin VM Stefani Stefano S Reissig Hans-Ulrich HU

Beilstein journal of organic chemistry 20131119

Herein we present the synthesis of the anhydrophytosphingosine jaspine B and three of its stereoisomers using a carbohydrate-derived alkoxyallene in order to obtain the products in enantiopure form. Key step of the reaction sequence is the addition of the lithiated alkoxyallene to pentadecanal, setting the configuration at the later C-2 of the ring system. This reaction step proceeds with moderate selectivity and therefore leads to a stereodivergent approach to the natural product and its enanti ...[more]

PMID: 24367420

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