Radical Cascade Transformations of Tris(o-aryleneethynylenes) into Substituted Benzo[a]indeno[2,1-c]fluorenes

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• 作者：Igor V. Alabugin ; Kerry Gilmore ; Satish Patil ; Mariappan Manoharan ; Serguei V. Kovalenko ; Ronald J. Clark ; Ion Ghiviriga
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：August 27, 2008
• 年：2008
• 卷：130
• 期：34
• 页码：11535-11545
• 全文大小：667K
• 年卷期：v.130,no.34(August 27, 2008)
• ISSN：1520-5126

文摘

Oligomeric o-aryleneethynylenes with three triple bonds undergo cascade radical transformations in reaction with a Bu₃SnH/AIBN system. These cascades involve three consecutive cycle closures with the formation of substituted benzo[a]indeno[2,1-c]fluorene or benzo[1,2]fluoreno[4,3-b]silole derivatives. The success of this sequence depends on regioselectivity of the initial attack of the Bu₃Sn radical at the central triple bond of the o-aryleneethynylene moiety. The cascade is propagated through the sequence of 5-exo-dig and 6-exo-dig cyclizations which is followed by either a radical attack at the terminal Ar substituent or radical transposition which involves H-abstraction from the terminal TMS group and 5-endo-trig cyclization. Overall, the transformation has potential to be developed into an approach to a new type of graphite ribbons.