CARBON-CHAIN EXTENSION THROUGH C-1 OF 2-DEOXYALDOSE DITHIOACETAL DERIVATIVES: A ROUTE TO 1,3-DIDEOXY-2-KETOSES

Article abstract of DOI:10.1016/0008-6215(80)90010-5

The 3,4:5,6-diisopropylidene acetal (3) of 2-deoxy-D-arabino-hexose underwent abstraction of H-1 by butyllithium in oxolane at -30 deg C; iodomethane reacted readily with the resultant anion to give the 1,3-dideoxy-2-heptulose derivative 4, and C-1 benzylation could likewise be effected.Attempted deacetonation of 4 gave mixtures, although 6,7-monodeacetonation could be achieved in high yield, affording access via glycol cleavage-reduction to the 1,3-dideoxy-2-hexulose derivative.Demercaptalation of 4 gave the acetal-protected 1,3-dideoxy-2-heptulose, which underwent methanolysis to give crystalline methyl 1,3-dideoxy- α-D-arabino-heptulopyranoside.Anions of the type derived from 3 have broad, synthetic potential for access to chainextended, 2-keto sugar derivatives of interest as metabolic intermediates, and for synthesis of deoxy analogs of such nucleoside antibiotics as psicofuranine and decoyinine.