Intramolecular direct aldol reactions of sugar diketones: syntheses of valiolamine and validoxylamine G.
A new and stereoselective intramolecular direct aldol reaction of diketones derived from carbohydrates has been developed to construct carbocycles with D-gluco-, D-galacto-, D-manno-, and L-ido-configurations. The stereochemical outcome of the aldol reaction of the diketone is dependent on the base used. Transformation of D-gluco-aldols readily affords valiolamine which also constitutes a formal synthesis of voglibose. Facile conversion of D-gluco-cyclohexanones into validoxylamine G has been achieved in 12 steps with 15.1% overall yield from D-glucose.
Shing
Tony K M
TK
Department of Chemistry and Center of Novel Functional Molecules, The Chinese University of Hong Kong, Shatin, Hong Kong, China. tonyshing@cuhk.edu.hk
Cheng
Hau M
HM
D000447:Aldehydes / Q000737:chemistry*; D002241:Carbohydrates / Q000737:chemistry*; D004791:Enzyme Inhibitors / Q000138:chemical synthesis; D065089:Glycoside Hydrolase Inhibitors; D007294:Inositol / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D007659:Ketones / Q000737:chemistry*; D050111:Imino Sugars
D000447:Aldehydes; D002241:Carbohydrates; D004791:Enzyme Inhibitors; D065089:Glycoside Hydrolase Inhibitors; D007294:Inositol; D007659:Ketones; C050693:validoxylamine G; C043270:valiolamine; D050111:Imino Sugars; C116609:3-hydroxybutanal; C102817:voglibose