MICROBIAL OXIDATION OF AROMATICS IN ENANTIOCONTROLLED SYNTHESIS .3. DESIGN OF AMINO CYCLITOLS (EXO-NITROGENOUS) AND TOTAL SYNTHESIS OF (+)-LYCORICIDINE VIA ACYLNITROSYL CYCLOADDITION TO POLARIZED 1-HALO-1,3-CYCLOHEXADIENES

Oxidation of halogenated benzenes with bacterial dioxygenase from Pseudomonas putida 39D (whole cell fermentation) provided homochiral 1,3-cyclohexadiene-cis-diols 1 for the entire halogen series. These compounds were investigated for their potential in cycloadditions with various dienophiles including propiolate, acylnitroso compounds, benzyne, quinones, and nitrile oxides. All cycloadducts formed with the regiochemistry predicted from molecular modeling. A brief synthesis of (+)-lycoricidine concluded the application of acylnitroso cycloadditions. New adducts of quinones and nitrile oxides were identified, and potential for these compounds in the synthesis of novel polycyclic oxygenated compounds is indicated. Experimental and spectral data are provided for all compounds.