Polyfunktionalisierte Cyclohexane aus Dianhydroinositen. cis ‐1,3(1,4)‐Inosadiamine aus Benzol

Abstract

Die Brauchbarkeit der aus Benzol gut zuganglichen Dianhydroinosite 4 -6 fur die Totalsynthese cis-l,4-bzw. cis-I ,3-disubstituierter Cyclohexantetrole wird exemplarisch belegt. Mit monovalenten Partnern (H20, HI, NaN,, NH2NH2) erfolgt die zweifache Epoxidoffnung jeweils regioselektiv (1,4-Disubstitution) zu den muco-bzw. chiro-Cyclohexan-Derivaten 9, 17 und 26. Mit Hydrazin bzw. N,N'-Dimethylhydrazin als 1,2-Dinucleophilen lassen sich aus 4/5 in guten Ausbeuten (75 -90%) die cis-l,3-Inosadiamine 7g (5-Epistreptamin) und 16g, j (2-Epistreptamin, Actinamin). aus dem weniger symmetrischen 6 in nur bescheidener Ausbeute (ca. 50%) ein Cemisch von 25g (Streptamin) und 27g herstellen. Die von 4 -6 ausgehenden Epoxidoffnungen sind kinetisch so wenig differenziert, da8 eine selektive Einfachoffnung nicht moglich ist.Polyfunctionalised Cyclohexanes from Dianhydroinositols. cis-l,3(1,4)-Inosadiamines from BenzeneThe preparative value of the dianhydroinositols 4 -6, which are readily available from benzene, for the total synthesis of cis-1,4-and cis-1.3-disubstituted cyclohexanetetrols is demonstrated. With monovalent reagents (H,O, HI, NaN,, NH2NH2) the twofold epoxide opening proceeds regioselectively (1,4-disubstitution) yielding the muco-and chiro-cyclohexane derivatives 9, 17, and 26. With hydrazine and N,N'-dimethylhydrazine as 1,2-dinucleophiles the cis-I ,3-inosadiamines 7g (5-epistreptamine) and 16g, j (2-epistreptamine, actinamine) are obtained from 4/5 in good yields . From the less symmetrical 6, however, only the mixture of 25g (streptamine) and 27g is produced in modest yield (ca. 50%). The epoxide opening reactions starting from 4 -6 are kinetically so similar that a selective opening is not possible.Im Zusammenhang mit der Synthese des cis-Trioxa-tris-o-homobenzols 3 (cis-,,Benzoltrioxid", Trisanhydro-cis-inosit) haben wir ein leistungsfahiges Verfahren fur die Herstellung der Epoxycyclohexenylbromide A bzw. B entwickelt (Schema 1)'). Damit waren neben 3 auch die Desoxydianhydroinosite*) (Dianhydroquercite) 1/2 und die Dianhydroinosite 4 -6 derart einfach und okonomisch aus Benzol zuganglich geworden'), daR ein breiter praparativer Einsatz im Bereich polyfunktionalisierter Cyclohexane und speziell fur Aminocyclit-Synthesen attraktiv wurde.

On the electronic effects of OH groups. Synthesis and investigation of tetrahydroxylated azabicycloheptanes

“…The most related compound reported in the literature was a protected derivative of 1 that was prepared by the Prinzbach group starting from cyclitol precursors. 19 While this compound could be prepared and deprotected, we selected a route that would allow us to obtain the molecules also possessing 2,3endo-diols from the same precursor. We chose the Diels-Alder adduct 4 (Scheme 1), which was obtained from the reaction of Boc-pyrrole (5) with tosylacetylene (6).…”

2-Oxoglycosyl (“Ulosyl”) and 2-Oximinoglycosyl Bromides: Versatile Donors for the Expedient Assembly of Oligosaccharides with β-d-Mannose, β-l-Rhamnose, N-Acetyl-β-d-mannosamine, and N-Acetyl-β-d-mannosaminuronic Acid Units

“…The broad spectrum antibiotic spectinomycin 176 can be perceived, in formal terms, to be a pseudodisaccharide in which a tricarbonyl sugar, the 4,6-dideoxy- d - glycero -hexose-2,3-diulose 177 designated actinospectose, is fused to N , N -methylated 1,3-diamino- myo -inositol actinamine 178 by both a β-glycosidic and a hemiketal linkage to form a pyran−dioxane−cyclohexane system in cis , cisoid , trans -arrangement. While actinamine 178 can readily be secured by acid hydrolysis of spectinomycin, and by a variety of syntheses, the actinospectose portion does not survive the harsh acidic conditions required for cleaving the bisglycosidic linkage (6 M HCl, 6 h reflux) and is left as an intractable tar.…”

2-Deoxystreptamine: Central Scaffold of Aminoglycoside Antibiotics

“…By the same sequence of steps, 44 could be converted to N,N′-diacetyl-2-deoxystreptamine (45) in an overall yield of 11%. Around a decade later, Prinzbach and coworkers [76][77][78] reported a synthesis of 2-deoxystreptamine starting by epoxidation of 1,4-cyclohexadiene (46, Scheme 10) with monoperphthalic acid (46 f 47). 79 Subsequent allylic bromination with Nbromosuccinimide in CCl 4 gives a 9:1 mixture of (the rather explosive) compounds trans-48 and cis-49.…”