Bhattacharya G, Su T L, Chia C M, Chen K T
Laboratory of Bioorganic Chemistry, Institute of Biomedical Sciences, Academia Sinica, Taipei 11529, Taiwan.
J Org Chem. 2001 Jan 26;66(2):426-32. doi: 10.1021/jo001020m.
The new tetracyclic 9H,10H-indolizino[1,2-b]indole-1-one derivatives (7a-d, 7ea, 7eb) have been synthesized by modified Fischer indole synthesis from the enol ether of 2,5-dihydroxy-7-methyl-6-cyano-indolizine (3) and arylhydrazines (4a-g). Attempted N-methylation of 7a-d produced a series of autoxidized products including 10-hydroperoxy-1-methoxyindolizino[1,2-b]indole (9a-d) as the major product accompanied with methylperoxides (10a-d and 11a-d) and 2-formyl-3-(pyridine-2-yl)indole (12a, 12c) derivatives as the minor products. A plausible mechanism of the autoxidation is postulated based on the isolation of some intermediates. The reaction is thought to proceed through azaenolate/enamine intermediates following a novel type of autoxidation.
新型四环9H,10H-中氮茚并[1,2-b]吲哚-1-酮衍生物（7a-d、7ea、7eb）通过改进的费歇尔吲哚合成法，由2,5-二羟基-7-甲基-6-氰基中氮茚（3）的烯醇醚与芳基肼（4a-g）合成。尝试对7a-d进行N-甲基化反应，得到了一系列自氧化产物，其中主要产物为10-氢过氧基-1-甲氧基中氮茚并[1,2-b]吲哚（9a-d），次要产物为甲基过氧化物（10a-d和11a-d）以及2-甲酰基-3-（吡啶-2-基）吲哚（12a、12c）衍生物。基于一些中间体的分离，推测了一个合理的自氧化机理。该反应被认为是通过氮杂烯醇盐/烯胺中间体进行的一种新型自氧化反应。
