D. Horton, K. Philips
Apr 1, 1972
Citations
0
Influential Citations
18
Citations
Journal
Carbohydrate Research
Abstract
Abstract The action of nitrous acid on methyl 2-amino-2-deoxy- d -gluconate hydrochloride ( 5 ) and acetylation of the product gives methyl 3,4,5,6-tetra- O -acetyl-2deoxy-2-diazo- d - arabino -hexonate ( 6 ); 4,6- O -benzylidene analogs of the methyl ( 4 ) and ethyl ( 3 ) esters are similarly prepared. Photolysis of the diazo sugar 6 in isopropyl alcohol gives mainly methyl 3,4,5,6-tetra- O -acetyl-2-deoxy- d - arabino -hexonate ( 13 ) and a small proportion of methyl 4,5,6-tri- O -acetyl-2,3-dideoxy- trans ,- d - erythro -hex2-enoate ( 14 ), whereas photolysis of 6 in methanol gave a cis,trans mixture of methyl 3,4,5,6-tetra- O -acetyl-2-deoxy- d -erythro-hex-2-enoate ( 10 ); the same mixture ( 10 ) of enol acetates was obtained by thermolysis of 6 . The diazo sugar 6 underwent cycloaddition with phenylacetylene to give a crystalline ( R or S )-3-( d - arabino -tetraacetoxybutyl)-3-methoxycarbonyl-5-phenyl-3 H -pyrazole ( 9 ) in 85% yield.