Reductive opening of carbohydrate phenylsulfonylethylidene (PSE) acetals. (19th November 2015)

• Record Type: Journal Article
• Authors: Chéry, Florence; Cabianca, Elena; Tatibouët, Arnaud; De Lucchi, Ottorino; Lindhorst, Thisbe K.; Rollin, Patrick
• Is Part Of: Carbohydrate research. Volume 417(2015)
• Page Start: 117
• Page End: 124
• Publication Date: 2015-11-19
• Subjects: Carbohydrate protecting groups -- Sulfones -- Phenylsulfonylethylidene (PSE) acetals -- Reductive desulfonylation -- SET -- Vinyl ethers; 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.2015.09.011
• Languages: English
• ISSNs: 0008-6215

Abstract

Highlights: Desulfonylation of carbohydrate phenylsulfonylethylidene (PSE) acetals is studied. Samarium iodide allows regioselective ring opening yielding 4-O-vinyl ethers. This reaction is applicable to a wide range of carbohydrate derivatives. PSE acetals might be useful as protective group. Graphical abstract: Abstract: The phenylsulfonylethylidene (PSE) acetal is a relatively new protecting group in carbohydrate chemistry. However, carbohydrate-derived phenylsulfonylethylidene (PSE) acetals show a different behavior in reductive desulfonylation than simple symmetrical acetals. Here we have investigated various SET-type reaction conditions in order to open PSE acetals regioselectively and to produce chiral ω-hydroxyethenyl ethers. Whereas sodium amalgam leads to a mixture of regioisomeric vinyl ethers besides the ethylidene acetal, samarium iodide is suited for regioselective ring opening. This is shown with seven different carbohydrate PSE acetals, both of the 1, 3-dioxane and the 1, 3-dioxolane type.