33818-52-9Relevant academic research and scientific papers
Pheromones, III: A Simple Method to Direct the Reduction of α-Alkoxy-carbonyl Compounds
Noe, Christian R.,Knollmueller, M.,Steinbauer, G.,Wagner, E.,Kuerner, H.,et al.
, p. 299 - 317 (2007/10/02)
Enantiomerically pure 1,2-diols bearing optionally syn or anti configurated secondary hydroxylic groups are synthesized from acetal-protected cyanohydrins.After resolution of the diastereomers the cyanohydrins are converted into α-alkoxy-ketones by Grignard-reaction followed by reduction using common chelating or non-chelating agents.Among others syntheses of enantiomerically pure pheromones, endo-Brevicomin, exo-Brevicomin and Dispalure are given as examples.
Metal-mediated decarbonylation and dehydration of ketose sugars
Andrews, Mark A.
, p. 2703 - 2708 (2008/10/08)
Ketose sugars can be decarbonylated and/or dehydrated by the action of certain metal complexes. Fructose reacts with 1 equiv of RhCl(PPh3)3 (1) in N-methyl-2-pyrrolidinone (NMP) at 130°C to give furfuryl alcohol, Rh(CO)Cl(PPh3)2 (2), and a small amount of 1-deoxyerythritol. 1,3-Dihydroxyacetone consumes 2 equiv of 1, giving methane and ca. 2 mol of 2. With manno-2-heptulose the primary product is 2,7-anhydromanno-2-heptulopyranose. The mechanisms of these unusual reactions have been studied by using 13C-labeling experiments and model reactions employing Pd(II) and HCl. Attempts to make the reactions catalytic using [Rh(Ph2PCH2CH2CH2PPh 2)2]+[BF4]- in place of 1 were not successful. The use of NMP as a solvent offers some advantages in the acid-catalyzed synthesis of certain carbohydrate dehydration products, as exemplified by the conversion of manno-2-heptulose to its 2,7-anhydride and of 2-deoxyglucose to 1-(2-furanyl)-1,2-ethanediol.
