Department of Chemistry , Indian Institute of Technology Madras , Chennai 600036 , Tamil Nadu , India.
J Org Chem. 2019 Dec 6;84(23):15590-15604. doi: 10.1021/acs.joc.9b02582. Epub 2019 Nov 25.
A rhodium(III)-catalyzed redox-neutral ring-opening of 7-azabenzonorbornadienes with aromatic ketoximes giving 2-arylated hydronaphthylamines in a highly diastereoselective manner is described. Later, the 2-arylated hydronaphthylamines were converted into highly sensitive 13,14-dehydro benzophenanthridine derivatives by HCl hydrolysis. Further, 13,14-dehydro benzophenanthridines were aromatized into biologically important benzophenanthridine derivatives in the presence of DDQ. A possible reaction mechanism was proposed and supported by deuterium labeling studies and isolation of a rhodacycle intermediate.
铑(III)催化的 7-氮杂苯并降冰片二烯与芳香酮肟的氧化还原中性开环反应，以高度非对映选择性的方式得到 2-芳基氢化萘胺。随后，2-芳基氢化萘胺通过 HCl 水解转化为高灵敏的 13,14-去氢苯并菲啶衍生物。进一步，在 DDQ 的存在下，13,14-去氢苯并菲啶衍生物芳构化为具有生物重要性的苯并菲啶衍生物。提出了一种可能的反应机制，并通过氘标记研究和铑环中间体的分离得到了支持。
