Controlling the Scholl Reaction

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• 作者：Benjamin T. King ; Ji//pubs.acs.org/images/entities/rcaron.gif" border="0">í ; Kroulí ; k ; Charles R. Robertson ; Pawel Rempala ; Cameron L. Hilton ; Justin D. Korinek ; Lisa M. Gort
• 刊名：Journal of Organic Chemistry
• 出版年：2007
• 出版时间：March 30, 2007
• 年：2007
• 卷：72
• 期：7
• 页码：2279 - 2288
• 全文大小：315K
• 年卷期：v.72,no.7(March 30, 2007)
• ISSN：1520-6904

文摘

Guidelines for the application of the Scholl reaction were developed. Labeling experiments demonstratethat the Scholl reaction fails in small, unsubstituted oligophenylenes (e.g., o-terphenyl) due tooligomerization of the products (e.g., triphenylene). Incorporation of suitably placed blocking groups(e.g., t-butyl) suppresses oligomerization. The well-established directing group effects in electrophilicaromatic substitution predict the outcome of Scholl reactions of substituted substrates. Activating o,p-directing groups (e.g., MeO) direct bond formation o,p, either intramolecularly or intermolecularly.Deactivating o,p-directing groups (e.g., Br) also direct bond formation o,p but yields are lower. Deactivatingm-directors (e.g., NO₂) suppress reaction. MoCl₅ and PhI(OOCCF₃)₂/BF₃·Et₂O are general and effectivereagents for the Scholl oxidation. Calculations (B3LYP/6-31G(d)) predict the Scholl reaction inalkoxyarenes to proceed via arenium cations, not radical cations. Suzuki-Miyaura couplings were usedto generate 12 substituted o-terphenyl derivatives.