Carbo- and heterocyclic nitroarenes react with anions of tert-butyl and cumyl hydroperoxides in the presence of strong bases to form substituted o- and p-nitrophenols. The reaction usually proceeds in high yields and is of practical value as a method of synthesis and manufacturing of nitrophenols. Orientation of the hydroxylation can be controlled to a substantial extent by selection of the proper conditions. Basic mechanistic features of this process were clarified.

The Iff-pyrrole derivative obtained from diethyl L-glutamate hydrochloride and tetrahydro-2,5-dimethoxyfuran was cyclized with BBr, to ethyl (5S)-5,6,7,8-tetrahydro-8-oxoindolizine-5-carboxylate (18). Catalytic hydrogenation of 18 over PdjC in AcOH gave ethyl (5S,8aR)-octahydroindolizine-5-carboxylate (21), whereas hydrogenation over Rh/AI,O, in EtOH/AcOH 99 : 1 afforded mainly ethyl (5S,8S,8aS)-octahydro-8-hydroxyindolizine-5-carboxylate (22). By functional-group interconversions, 21 was transformed into piclavine A (1) and indolizidine 209D (2). Similarly, (5R,8R,8aS)-octahydro-5-pentylindolizine-8-methanol (37), the final relay for indolizidine 209B (3), was obtained from 22.Introduction. -Indolizidine ( = octahydroindolizine) alkaloids attract attention because of their diverse biological properties and scarce occurrence in exotic organisms [ 13. Of particular relevance are the 5-alkyl-and 5,8-dialkylindolizidines which, despite their seemingly simple structures, are not easy to prepare in an enantiomerically pure state. A typical example is piclavine A (l), an antimicrobial constituent extracted from the tunicate Clavelina picta, which represents the first indolizidine occurring in the marine biosphere [2]. Equally typical are the highly toxic indolizidines 209D') (2) and 209B (3) which were isolated in infinitesimally small amounts from the skin of neotropical frogs of the Dendrobatidue family [4] [5]. Several approaches to 2 and 3 have been undertaken, whereas 1 has yet to be synthesized. The stereochemical problem centers on the construction of the bicyclic entity of the desired configuration at the C(5) and C(8a) positions and, in the case of 3, the creation of the trans-disposed Me group. A variety of solutions have been propounded. Most make use of chiral auxiliaries, whereas some exploit optically active starting materials of natural origin which were incorporated to various degrees in the final product [&lo]. However, they usually require many steps and, with few exceptions, are characterized by low yields.

No abstract

No abstract