88548-50-9Relevant academic research and scientific papers
Metal-mediated decarbonylation and dehydration of ketose sugars
Andrews, Mark A.
, p. 2703 - 2708 (1989)
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.
Five-coordinate dicarbonyl complexes of rhodium(I): (X = Cl, Br, I)
Sanger, Alan R.
, p. 571 - 575 (2007/10/02)
The complexes trans- (1, X = Cl, Br, I) react with CO to form (2), and not to form cis-.Complexes 2 contain equivalent axial carbonyl ligands.It is proposed that a series of dicarbonyl complexes, including 2, is formed during decarbonylation reactions catalyzed by 1.
