Ti/Ni-Mediated Inter- and Intramolecular Conjugate Addition of Aryl and Alkenyl Halides and Triflates

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• 作者：Irene R. Márquez ; Delia Miguel ; Alba Millán ; M. Luisa Marcos ; Luis álvarez de Cienfuegos ; Araceli G. Campa?a ; Juan M. Cuerva
• 刊名：Journal of Organic Chemistry
• 出版年：2014
• 出版时间：February 21, 2014
• 年：2014
• 卷：79
• 期：4
• 页码：1529-1541
• 全文大小：526K
• ISSN：1520-6904

文摘

In this work, we show that the unique combination of a nickel catalyst and Cp₂TiCl allows the direct conjugate addition of aryl and alkenyl iodides, bromides, and to a lesser extent, chlorides and triflates to 伪,尾-unsaturated carbonyls at room temperature, without requiring the previous formation of an organometallic nucleophile. The reaction proceeds inter- and intramolecularly with good functional group compatibility, which is key for the development of free protecting group methodologies. Carbo- and heterocycles of five- and six-membered rings are obtained in good yields. Moreover, some insights about the mechanism involved have been obtained from cyclic voltammetry, UV鈥搗is, and HRTEM measurements.