Synthesis and reactivity of nonstabilized diazo sugars.
1,6-Anhydro-4-deoxy-4-diazo-2,3-O-isopropylidene-beta-D-lyxo-hexopyranose (4) is a stable crystalline compound readily accessible by an improved synthetic procedure. It has been used as a model for evaluating the reactivity of the diazo group, when not stabilized by an adjacent carbonyl function, in a rigid chiral matrix. A range of carbene-type, electrophile-promoted, and 1,3-dipolar reactions were evaluated, leading to 4,4'-alkene dimers, 4-deoxy-3-enose and related derivatives, 4,4-dihalo compounds, 4-spirocyclopropane derivatives, 4-spiropyrazole structures, and by skeletal rearrangement, branched-chain anhydropentose structures having a bicyclo[2.2.2] skeleton.
Alexander
Michael S
MS
Department of Chemistry, American University, 4400 Massachusetts Avenue, NW, Washington, DC 20016, USA.
Horton
Derek
D
D001391:Azo Compounds / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism*; D002236:Carbohydrate Conformation; D004187:Disaccharides / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism; D008968:Molecular Conformation; D015394:Molecular Structure
D001391:Azo Compounds; D004187:Disaccharides