The development of novel strategies for the synthesis of carbohydrate mimics is a major task in modern bioorganic and medicinal chemistry.1Besides traditional approaches especially domino reactions which have the potential to build up a high degree of complexity in only a few steps have come into the focus in the recent past.The talk will discuss how cyclopropanes as well as carbon-carbon triple bonds, both being systems which are high in energy are utilized to trigger a cascade of consecutive reactions starting from carbohydrates. Carbopalladation reactions are used to synthesize chromans and isochromans starting from bromoglycals.2 Cyclopropanated sugars showing a highly reactive donor-acceptor cyclopropane3 are converted via a domino sequence consisting of oxidation and ring-enlargement into spiroketals.4In addition to spiroketal formation the talk will demonstrate in which way a spiroannulated three-membered having only minimal impact on the structural integrity of the carbohydrate, reduces the rotational flexibility of the C6-O bond.5Corresponding syntheses for building blocks and their behavior in glycosylation reactions will be discussed. 1) Review on carbohydrate mimics: Koester, D. C.; Holkenbrink, A.; Werz, D. B. Synthesis 2010  , 3217-3242. 2) (a) Leibeling, M.; Koester, D. C.; Pawliczek, M.; Schild, S. C.; Werz, D. B. Nature Chem. Biol. 2010  , 6, 199-201. (b) Leibeling, M.; Milde, B.; Kratzert, D.; Stalke, D.; Werz, D. B. Chem. Eur. J. 2011  , 17, 9888-9892. 3) Schneider, T. F.; Kaschel, J.; Werz, D. B. Angew. Chem. Int. Ed. 2014  , 53, in press. 4) Brand, C.; Rauch, G.; Zanoni, M.; Dittrich, B.; Werz, D. B. J. Org. Chem. 2009  , 74, 8779-8786. 5) (a) Brand, C.; Granitzka, M.; Stalke, D.; Werz, D. B. Chem. Commun. 2011  , 47, 10782-10784. (b) Brand, C.; Kettelhoit, K.; Werz, D. B. Org. Lett. 2012  , 14, 5126-5129.

Adventures with sugars, three-membered rings, and triple bonds

248th National Meeting (2014)

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