Photoamidation of 3,4,6-Tri-O-acetyl-1,2-dideoxy-D-arabino-hex-1-enopyranose

Abstract

The acetone-initiated photochemical addition of formamide to 3,4,6-tri-O-acetyl-1,2-dideoxy-D-arabino-hex-1-enopyranose (1) afforded 3,4,6-tri-O-acetyl-2,6-anhydro-3-deoxy-D-gluco-heptonamide (2), 3,4,6-tri-O-acetyl-2,6-anhydro-3-deoxy-D-manno-heptonamide (3), and3,4,6-tri-O-acetyl-1,5-anhydro-2-C-carbamoyl-1,2-dideoxy-D-gluco-hexitol (4) in a combined yield of about 75% (the ratio of yields of 2,3, and 4 was approximately 2:2:3). In addition, trace quantities of the epimeric manno branched-chain adduct of 4, and acetone adducts of 1 were formed. Lithium aluminum hydride reduction of 4 yielded a branched-chain aminopolyol, isolated as its N-acetyl derivative.