Amadori ketoses with calcium hydroxide and the Kiliani reaction on 1-deoxy ketoses: two approaches to the synthesis of saccharinic acids

Abstract

Saccharinic acids (2- C-methyl aldonic acids) may be formed by treatment of Amadori ketoses with calcium hydroxide or by the Kiliani reaction of 1-deoxy ketoses with cyanide. Thus (i) N, N-dibenzyl or N, N-dimethyl-1-amino-1-deoxy- d-fructose with aqueous calcium hydroxide afforded 2- C-methyl- d-ribono-1,4-lactone under green conditions and (ii) reaction of methyl magnesium bromide with 2,3- O-isopropylidene- d-erythronolactone gave 1-deoxy-3,4- O-isopropylidene- d-ribulose, which on subsequent treatment with aqueous sodium cyanide and hydrolysis, formed 2- C-methyl- d-arabinono-1,4-lactone. Such branched sugar lactones are likely to be of value as chirons containing branched carbon chains.