Phenanthrene Synthesis by Iron-Catalyzed [4+2] Benzannulation between Alkyne and Biaryl or 2-Alkenylphenyl Grignard Reagent
Phenanthrene Synthesis by Iron-Catalyzed [4+2] Benzannulation between Alkyne and Biaryl or 2-Alkenylphenyl Grignard Reagent
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DOI：
10.1021/ja201931e
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发表时间：
2011-05-04
影响因子：
15
通讯作者：
Nakamura, Eiichi
中科院分区：
文献类型：
--
作者：
Matsumoto, Arimasa;Ilies, Laurean;Nakamura, Eiichi
在Fe(acac) 3,4,4′-二叔丁基-2,2′-联吡啶基和1,2 -二氯-2-甲基丙烷存在下，内炔或端炔与2-联芳基、2-杂芳基苯基或2-烯基苯基格氏试剂在室温下1 h内发生[4 + 2]苯环化反应，得到9-取代或9,10-二取代的菲及其同系物，产率中等至优异。该反应耐受敏感官能团，如溴和烯烃。当作用于1,3-二炔时，在两个乙基上发生环化反应，得到双菲衍生物。
The [4 + 2] benzannulation reaction of internal or terminal alkynes with 2-biaryl, 2-heteroarylphenyl, or 2-alkenylphenyl Grignard reagents in the presence of Fe(acac)3, 4,4'-di-tert-butyl-2,2'-bipyridyl, and 1 ,2-dichloro-2-methylpropane takes place at room temperature in I h to give 9-substituted or 9,10-disubstituted phenanthrenes and congeners in moderate to excellent yields. The reaction tolerates sensitive functional groups such as bromide and olefin. When applied to a 1,3-diyne, the annulation reaction takes place on both acetylenic moieties to give a bisphenanthrene derivative.