Rh^II-Catalyzed β-C(sp²)−H Alkylation of Enol Ethers, Enamides and Enecarbamates with α-Diazo Dicarbonyl Compounds

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• 作者：Brett D. McLarney ; Marchello A. Cavitt ; Theodore M. Donnell ; Dr. Djamaladdin G. Musaev and Prof. Dr. Stefan France
• 刊名：Chemistry - A European Journal
• 出版年：2017
• 出版时间：January 23, 2017
• 年：2017
• 卷：23
• 期：5
• 页码：1129-1135
• 全文大小：2700K
• ISSN：1521-3765

文摘

A Rh^II-catalyzed method for intermolecular alkylation of the β-C(sp²)−H bond of enol ethers, enamides, and enecarbamates with α-diazo-1,3-dicarbonyl compounds is reported. The products are formed in up to 99 % yield and can be readily derivatized under a variety of conditions. By utilizing a combination of experimental and computational studies, the presumptive addition–elimination reaction mechanism was investigated and found to proceed under thermodynamic control at higher temperature. The acquired fundamental knowledge was translated into a strategic reaction design and yielded the first example of the β-C−H functionalizations of acyclic enol ethers using α-diazo-1,3-dicarbonyl compounds.