title: Synthesis and Applications of Silyl 2-Methylprop-2-ene-1-sulfinates in Preparative Silylation and GC-Derivatization Reactions of Polyols and Carbohydrates.
abstract: Trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, and triisopropylsilyl 2-methylprop-2-ene-1-sulfinates were prepared through (CuOTf)2⋅C6H6-catalyzed sila-ene reactions of the corresponding methallylsilanes with SO2 at 50 °C. Sterically hindered, epimerizable, and base-sensitive alcohols gave the corresponding silyl ethers in high yields and purities at room temperature and under neutral conditions. As the byproducts of the silylation reaction (SO2 +isobutylene) are volatile, the workup was simplified to solvent evaporation. The developed method can be employed for the chemo- and regioselective semiprotection of polyols and glycosides and for the silylation of unstable aldols. The high reactivity of the developed reagents is shown by the synthesis of sterically hindered per-O-tert-butyldimethylsilyl-α-D-glucopyranose, the X-ray crystallographic analysis of which is the first for a per-O-silylated hexopyranose. The per-O-silylation of polyols, hydroxy carboxylic acids, and carbohydrates with trimethylsilyl 2-methylprop-2-ene-1-sulfinate was coupled with the GC analysis of nonvolatile polyhydroxy compounds both qualitatively and quantitatively.
authors: Laboratoire de glycochimie et de synthèse asymétrique, Swiss Federal Institute of Technology of Lausanne (EPFL), Lausanne, 1015, Switzerland), Fax: (+41) 21-693-93-55. dmarkovic@kemija.unios.hr.|Chemistry Department, University of Osijek, Osijek, Ulica cara Hadrijana 8A, Croatia, 31000. dmarkovic@kemija.unios.hr.|Department of Biotechnology, University of Rijeka, Radmile Matejčić 2, 51000, Rijeka, Croatia. dmarkovic@kemija.unios.hr.
authors: Dean
authors: D
authors: Marković
authors: Laboratoire de glycochimie et de synthèse asymétrique, Swiss Federal Institute of Technology of Lausanne (EPFL), Lausanne, 1015, Switzerland), Fax: (+41) 21-693-93-55.
authors: Wandji Augustin
authors: WA
authors: Tchawou
authors: Faculty of Materials Science and Applied Chemistry, Riga Technical University, P. Valdena Str. 3, Riga, 1007, Latvia.
authors: Irina
authors: I
authors: Novosjolova
authors: Laboratoire de glycochimie et de synthèse asymétrique, Swiss Federal Institute of Technology of Lausanne (EPFL), Lausanne, 1015, Switzerland), Fax: (+41) 21-693-93-55.
authors: Sylvain
authors: S
authors: Laclef
authors: Faculty of Materials Science and Applied Chemistry, Riga Technical University, P. Valdena Str. 3, Riga, 1007, Latvia.|Latvian Institute of Organic Synthesis, Aizkraukles Str. 21, Riga, 1006, Latvia.
authors: Dmitrijs
authors: D
authors: Stepanovs
authors: Faculty of Materials Science and Applied Chemistry, Riga Technical University, P. Valdena Str. 3, Riga, 1007, Latvia. maris_turks@ktf.rtu.lv.
authors: Māris
authors: M
authors: Turks
authors: Laboratoire de glycochimie et de synthèse asymétrique, Swiss Federal Institute of Technology of Lausanne (EPFL), Lausanne, 1015, Switzerland), Fax: (+41) 21-693-93-55. pierre.vogel@epfl.ch.
authors: Pierre
authors: P
authors: Vogel
mesh_terms: D000438:Alcohols / Q000737:chemistry; D002241:Carbohydrates / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry; D002384:Catalysis; D004987:Ethers / Q000737:chemistry; D006601:Hexoses / Q000737:chemistry; D011108:Polymers / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D012997:Solvents; D013441:Sulfinic Acids / Q000737:chemistry*
chemical_list: D000438:Alcohols; D002241:Carbohydrates; D002264:Carboxylic Acids; D004987:Ethers; D006601:Hexoses; D011108:Polymers; D012821:Silanes; D012997:Solvents; D013441:Sulfinic Acids; C024617:polyol
keywords: chemoselectivity; gas chromatography; regioselectivity; silyl sulfinates; silylation