Enantioselective de Novo Synthesis of 4-Deoxy-d-hexopyranoses via Hetero-Diels鈥揂lder Cycloadditions: Total Synthesis of Ezoaminuroic Acid and Neosidomycin

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• 作者：Denis Gigu猫re ; Julien Martel ; Tze Chieh Shiao ; Ren茅 Roy
• 刊名：Journal of Organic Chemistry
• 出版年：2011
• 出版时间：December 2, 2011
• 年：2011
• 卷：76
• 期：23
• 页码：9687-9698
• 全文大小：556K
• 年卷期：v.76,no.23(December 2, 2011)
• ISSN：1520-6904

文摘

The de novo synthesis of carbohydrates constitutes an important aspect of organic chemistry, and its application toward deoxy sugars is particularly noteworthy in targeting biologically active compounds. The enantioselective preparation of 4-deoxy-d-ribo-, 4-deoxy-d-lyxo-, and 4-deoxy-d-xylo-hexopyranosides, along with their uronate counterparts has been successfully accomplished using hetero-Diels鈥揂lder reactions as the key step. Jacobsen chromium(III) catalyst and a titanium鈥揵inaphthol complex have been used to successfully catalyze diene and aldehyde cycloadditions, leading to optically active dihydropyran templates. 6-Hydroxydesosamine, orthogonally protected ezoaminuroic acid, and neosidomycin were synthesized using a comparative study. Also, a novel chiron approach to 4-deoxy-lyxo-hexopyranosiduronic acid methyl ester derivatives was efficiently accomplished starting from readily accessible starting materials. This work represents a systematic and comprehensive study toward a de novo synthesis of 4-deoxy-hexopyranoses via enantioselective hetero-Diels鈥揂lder reactions.