Iridium-Catalyzed Annulative Coupling of 2-Arylbenzoyl Chlorides with Alkynes: Selective Formation of Phenanthrene Derivatives

详细信息    查看全文

• 作者：Tomoya Nagata ; Koji Hirano ; Tetsuya Satoh ; Masahiro Miura
• 刊名：Journal of Organic Chemistry
• 出版年：2014
• 出版时间：October 3, 2014
• 年：2014
• 卷：79
• 期：19
• 页码：8960-8967
• 全文大小：471K
• ISSN：1520-6904

文摘

2-Arylbenzoyl chlorides undergo annulative coupling with internal alkynes in the presence of a catalyst system of [IrCl(cod)]₂/P(t-Bu)₃ to selectively afford the corresponding phenanthrene derivatives accompanied by elimination of carbon monoxide and hydrogen chloride. The reaction occurs without addition of any external base. Deuterium-labeling experiments using 2-(d₅-phenyl)benzoyl chloride suggest that the rate-determining step does not involve the C2鈥测€揌 bond cleavage. Formation of a [(t-Bu)₃PH][(biphenyl-2,2鈥?diyl)Ir(CO)Cl₂] complex dimer, of which the structure was determined by single-crystal X-ray analysis, from a stoichiometric reaction at 60 掳C without addition of alkyne also supports the facile C鈥揌 cleavage.