SYNTHESIS OF 1- AND 3-C-(AMINOMETHYL)-1,2,3,4,5-CYCLOHEXANEPENTOLS FROM (+)-epi-QUERCITOL[1]

Oxidation of three di-O-isopropylidene derivatives 2a—4a, newly derived from (+)-epi-quercitol (1), with acetic anhydride in DMSO gave the corresponding ketones 5—7, which underwent aldol-type condensation with nitromethane under basic conditions to give selectively the protected derivatives 8a—10a of C-nitromethyl-1,2,3,4,5-cyclohexanepentols, respectively. On treatment with diazomethane in DMSO, the ketones 6 and 7 gave single spiro epoxides 11 and 12, the structures of which were confirmed by converting them into new C-(azidomethyl)cyclohexanepentols 16 and 17. The nitro compounds were hydrogenated in the presence of Raney nickel to give the amines isolated as the N-acetyl derivatives. Deprotection gave three new 1- and 3-C-aminomethyldeoxyinositols 15c—17c. The aminocyclitols obtained and their N-acetyl derivatives were assayed for inhibitory activity against examples of glycosidases.