| Title: | Synthesis and Applications of Silyl 2-Methylprop-2-ene-1-sulfinates in Preparative Silylation and GC-Derivatization Reactions of Polyols and Carbohydrates |
| Author(s): | Markovic D; Tchawou WA; Novosjolova I; Laclef S; Stepanovs D; Turks M; Vogel P; |
| Address: | "Laboratoire de glycochimie et de synthese asymetrique, 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 Matejcic 2, 51000, Rijeka, Croatia. dmarkovic@kemija.unios.hr. Laboratoire de glycochimie et de synthese asymetrique, Swiss Federal Institute of Technology of Lausanne (EPFL), Lausanne, 1015, Switzerland), Fax: (+41) 21-693-93-55. 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. Faculty of Materials Science and Applied Chemistry, Riga Technical University, P. Valdena Str. 3, Riga, 1007, Latvia. maris_turks@ktf.rtu.lv. Laboratoire de glycochimie et de synthese asymetrique, Swiss Federal Institute of Technology of Lausanne (EPFL), Lausanne, 1015, Switzerland), Fax: (+41) 21-693-93-55. pierre.vogel@epfl.ch" |
| ISSN/ISBN: | 1521-3765 (Electronic) 0947-6539 (Linking) |
| Abstract: | "Trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, and triisopropylsilyl 2-methylprop-2-ene-1-sulfinates were prepared through (CuOTf)2?naC6H6-catalyzed sila-ene reactions of the corresponding methallylsilanes with SO2 at 50 degrees 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-alpha-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" |
| Keywords: | Alcohols/chemistry Carbohydrates/*chemistry Carboxylic Acids/chemistry Catalysis Ethers/chemistry Hexoses/chemistry Polymers/*chemistry Silanes/*chemistry Solvents Sulfinic Acids/*chemistry chemoselectivity gas chromatography regioselectivity silyl sulfin; |
| Notes: | "MedlineMarkovic, Dean Tchawou, Wandji Augustin Novosjolova, Irina Laclef, Sylvain Stepanovs, Dmitrijs Turks, Maris Vogel, Pierre eng Research Support, Non-U.S. Gov't Germany 2016/02/13 Chemistry. 2016 Mar 14; 22(12):4196-205. doi: 10.1002/chem.201504380. Epub 2016 Feb 11" |
