Stereoselective syntheses of 3-aminocyclooctanetriols and halocyclooctanetriols

Abstract

The efficient synthesis of two new stereoisomeric 3-aminocyclooctanetriols and their new halocyclitol derivatives starting from cis,cis-1,3-cyclooctadiene are reported. Reduction of cyclooctene endoperoxide, obtained by photooxygenation of cis,cis-1,3-cyclooctadiene, with zinc yielded a cyclooctene diol followed by acetylation of the hydroxy group, which gave dioldiacetate by OsO4/NMO oxidation. The cyclooctane dioldiacetate prepared was converted to the corresponding cyclic sulfate via the formation of a cyclic sulfite in the presence of catalytic RuO4. The reaction of this cyclic sulfate with a nucleophilic azide followed by the reduction of the azide group provided the target, 3-aminocyclooctanetriol. The second key compound, bromotriol, was prepared by epoxidation of the cyclooctenediol with m-chloroperbenzoic acid followed by hydrolysis with HBr(g) in methanol. Treatment of bromotriol with NaN3 and the reduction of the azide group yielded the other desired 3-aminocyclooctanetriol. Hydrolysis of the epoxides with HCl(g) in methanol gave stereospecifically new chlorocyclooctanetriols.

Efficient and regioselective synthesis of dihydroxy-substituted 2-aminocyclooctane-1-carboxylic acid and its bicyclic derivatives

“…Therefore, we were inspired to develop new methods for the synthesis of hydroxylated β-amino acid derivatives containing eight-membered rings. We have recently reported the synthesis of various eight-membered aminocyclitols and their derivatives [19][20][21][22][23][24][25]. In the present paper, we describe the synthesis of some hydroxyl-ated β-amino acid derivatives containing eight-membered rings starting from cis,cis-1,3-cyclooctadiene.…”

Efficient synthesis of aziridinecyclooctanediol and 3-aminocyclooctanetriol

“…Many groups have described different synthetic methods for the synthesis of various aminocyclitols [13][14][15][16][17]. However, only few synthetic methods are available for the synthesis of eight-membered [18][19][20][21][22][23][24][25][26][27][28][29] aminocyclitols. On the other hand, the synthesis of a C8-cyclitol derivative containing the aziridine ring has not yet been reported.…”

“…On the other hand, the synthesis of a C8-cyclitol derivative containing the aziridine ring has not yet been reported. Therefore, in our continued efforts for efficient syntheses of cyclitols [30][31][32][33] and C8-aminocyclitols [18][19][20][21][22][23][24], we were interested in developing an efficient synthesis of aziridinecyclooctanediol. In the present paper, we report the efficient synthesis of aziridinecyclooctanediol and a new 3-aminocyclooctanetriol stereoisomer starting from cis,cis-1,3cyclooctadiene.…”