Stereoselective syntheses of 3-aminocyclooctanetriols and halocyclooctanetriols.

Emine Salamci,Yunus Zozik

doi:10.3762/bjoc.17.59

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.

Highlights

The synthesis of aminocyclitols has attracted attention because they contain substructures of many biologically active natural products [1,2,3]
As part of our work involving the synthesis of C8-cyclitols, we report the stereospecific syntheses of two new 3-aminocyclooctanetriols and some chlorinated C8-cyclitols starting from cis,cis-1,3-cyclooctadiene
For the synthesis of amino- and chlorocyclitols and their derivatives, we first selected endoperoxide 5 as the starting molecule, which was prepared using a procedure described in the literature [33] (Scheme 1)

Summary

Introduction

The synthesis of aminocyclitols has attracted attention because they contain substructures of many biologically active natural products [1,2,3]. Many methods have been previously reported for the synthesis of aminocyclitols containing five- and six-membered rings, along with their diverse biological activities [1,2,3,16,17,18,19,20,21,22,23,24,25,26].

Results

Conclusion