Developing cellulosic waste products as platform chemicals: protecting group chemistry of α-glucoisosaccharinic acid. (2nd January 2018)

• Record Type: Journal Article
• Authors: Almond, Michael; Suleiman, Mustapha G.; Hawkins, Matthew; Winder, Daniel; Robshaw, Thomas; Waddoups, Megan; Humphreys, Paul N.; Laws, Andrew P.
• Is Part Of: Carbohydrate research. Volume 455(2017)
• Page Start: 97
• Page End: 105
• Publication Date: 2018-01-02
• Subjects: Saccharinic acids -- Isosaccharinic acid -- Glucoisosaccharinic acid -- Protecting groups; Carbohydrates -- Periodicals; Chemistry, Organic -- Periodicals; Biochemistry -- Periodicals; Carbohydrates -- Periodicals; Chimie organique -- Périodiques; Glucides -- Périodiques; Biochemistry; Carbohydrates; Chemistry, Organic; Periodicals; Electronic journals; 507.78
• DOI: 10.1016/j.carres.2017.11.013
• Languages: English
• ISSNs: 0008-6215

Abstract

Abstract: Alpha and beta-glucoisosaccharinic acids ((2 S, 4 S )-2, 4, 5-trihydroxy-2-(hydroxymethyl)pentanoic acid and (2 R, 4 S )-2, 4, 5-trihydroxy-2-(hydroxymethyl)pentanoic acid) which are produced when cellulosic materials are treated with aqueous alkali are potentially valuable platform chemicals. Their highly functionalised carbon skeleton, with fixed chirality at C-2 and C-4, makes them ideal starting materials for use in synthesis. In order to assess the potential of these saccharinic acids as platform chemicals we have explored the protecting group chemistry of the lactone form of alpha-glucoisosaccharinic acid (α-GISAL). We report here the use of single and multiple step reaction pathways leading to the regioselective protection of the three different hydroxyl groups of α-GISAL. We report strategies for protecting the three different hydroxyl groups individually or in pairs. We also report the synthesis of a range of tri-O-protected α-GISAL derivatives where a number of the products contain orthogonal protecting groups. Graphical abstract: Highlights: Synthesis of novel bis-5, 6-di- O- protected-α-glucoisosaccharinic acid derivatives. Synthesis of novel tris-2, 5, 6-tri-O-protected-α-glucoisosaccharinic acid derivatives. Synthesis of 5, 6-di- O- protected α-glucoisosaccharinic acids with orthogonal protection. Synthesis of novel cyclic-2, 6-di-O-protected α-glucoisosaccharinic acid derivatives. Synthesis of novel cyclic-5, 6-di-O-protected α-glucoisosaccharinic acid derivatives.