Ferrier rearrangement promoted by an electrochemically generated zirconium catalyst.
In situ generated zirconium catalyst from a sacrificial zirconium anode was successfully applied to promote Ferrier rearrangement of 3,4,5-tri-O-acetyl-D-glucal and 6-deoxy-3,4-di-O-acetyl-L-glucal (3,4-di-O-acetyl-L-rhamnal) in the presence of three thiols and eleven thiophenols as nucleophiles. A simple constant current electrolysis (20 mA, 0.4 F mol(-1)) of an acetonitrile solution of lithium perchlorate (0.1 M) containing the corresponding glycal and S-nucleophiles, using a zirconium anode and a platinum cathode resulted in the successful synthesis of the corresponding 2,3-unsaturated peracetylated thioglycosides (with an average anomer ratio α/β=4.129 in the case of peracetylated D-glucal and 8.740 in the case of L-rhamnal). The same procedure proved to be appropriate in synthesizing dihydropyran derivatives ('C-glycosides') using allyltrimethylsilane as the nucleophile (only 'α-anomers' were obtained). All new compounds were fully characterized by spectral data, whereas single-crystal X-ray analysis was performed for two thioglycosides.
Department of Chemistry, Faculty of Science, University of Kragujevac, R. Domanovića 12, 34000 Kragujevac, Serbia.
Dragana
D
Stevanović
Department of Chemistry, Faculty of Science, University of Kragujevac, R. Domanovića 12, 34000 Kragujevac, Serbia.
Anka
A
Pejović
Department of Chemistry, Faculty of Science, University of Kragujevac, R. Domanovića 12, 34000 Kragujevac, Serbia.
Ivan
I
Damljanović
Department of Chemistry, Faculty of Science, University of Kragujevac, R. Domanovića 12, 34000 Kragujevac, Serbia.
Aleksandra
A
Minić
Vinča Institute of Nuclear Sciences, Laboratory of Theoretical Physics and Condensed Matter Physics, University of Belgrade, PO Box 522, 11001 Belgrade, Serbia.
Goran A
GA
Bogdanović
Department of Pharmacy, Faculty of Medicine, University of Kragujevac, S. Markovića 69, 34000 Kragujevac, Serbia.
Mirjana
M
Vukićević
Department of Chemistry, Faculty of Science and Mathematics, University of Niš, Višegradska 33, 18000 Niš, Serbia. Electronic address: nikoradulovic@yahoo.com.
Niko S
NS
Radulović
Department of Chemistry, Faculty of Science, University of Kragujevac, R. Domanovića 12, 34000 Kragujevac, Serbia. Electronic address: vuk@kg.ac.rs.
Rastko D
RD
Vukićević
D002236:Carbohydrate Conformation; D002384:Catalysis; D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D010984:Platinum / Q000737:chemistry; D013865:Thioglycosides / Q000138:chemical synthesis* / Q000737:chemistry; D015040:Zirconium / Q000737:chemistry*
D013865:Thioglycosides; D010984:Platinum; D015040:Zirconium
Anodic generation of catalyst; Peracetylated d-glucal; Peracetylated l-rhamnal; Pseudoglycals; Thiophenols; Zirconium