Ruthenium(II)-Catalyzed C–H Functionalization Using the Oxazolidinone Heterocycle as a Weakly Coordinating Directing Group: Experimental and Computational Insights

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• 作者：Jamie A. Leitch ; Philippe B. Wilson ; Claire L. McMullin ; Mary F. Mahon ; Yunas Bhonoah ; Ian H. Williams ; Christopher G. Frost
• 刊名：ACS Catalysis
• 出版年：2016
• 出版时间：August 5, 2016
• 年：2016
• 卷：6
• 期：8
• 页码：5520-5529
• 全文大小：798K
• 年卷期：0
• ISSN：2155-5435

文摘

Herein, we report the ruthenium-catalyzed ortho C–H alkenylation of a wide range of N-aryloxazolidinone scaffolds. Alkenylation was achieved with complete monoselectivity with a scope of 27 examples in 2-MeTHF. Yields ranged from 23 to 94%, producing highly decorated oxazolidinone scaffolds. A kinetically relevant C–H cleavage was also observed with a kinetic isotope effect (KIE) of ∼2. Density functional theory calculations provided information about mechanism, detailing the β-hydride elimination as the most energetically challenging step of 13.5 kcal mol^–1. In-depth computational kinetic studies also predicted a KIE of 2.17 for C–H cleavage and an intrinsic KIE for the reaction of 2.22, in line with the experimentally observed value.