Aminocyclitols. XXIX. Synthesis of Inosadiamines via 1,3-Biimino-1,3-dideoxy-inositols

Abstract

Hydrazinolysis of Dl-1,4-dibromo-1,4-dideoxy-chiro-inositol (3a), followed by catalytic hydrogenation and acetylation, afforded di-N-acetyl-tetra-O-acetyl-neo-inosadiamine-1,3 (6a) and -scyllo-inosadiamine-1,3 (7) in 18% and 24% yields, respectively. From the intact hydrazinolyzate of 3a, two new stereoisomeric 1,3-biimino-1,3-dideoxy-inositols (4a and 5a) could be isolated, and their structures were established by correlating to the corresponding inosadiamines. A similar hydrazinolysis of 3,6-di-O-p-tolylsulfonyl-muco-inositol (12) gave sole crystalline 1,3-biimino compound (13a), whose structure was followed from its conversion into known di-N-acetyltetra-O-acetyl-myo-inosadiamine-4,6 (14). PMR spectra of four 1,3-biimino compounds were discussed.

Chemistry of cis‐Trioxatris‐σ‐homobenzene. A Simple Total Synthesis of Streptamine

“…61 1 ; route B was preferred. [7] With Grignard reagents available only in tetrahydrofuran the reaction gives only poor yields.…”

“…297°C (decomp.)). Treatment of (8) with 5~ Br Br NaOH (molar ratio 1 :6, 90min, iW"C) yields the readily soluble hydrazine compound (9) [7] ; hydrogenolysis of ( 9 ) over Raney nickel affords streptamine (IOU). (IOa) was precipitated as the sulfate and identified as the hexaacetate The pressure reaction necessary for the hydrolysis (7) 4 (8) can be circumvented by resorting to a slightly different route in which the pyridazinedione ( 1 2 ) (faint yellow crystals, m.p.…”