Fatemeh Khamespanah, James B. Gerken, David S. Mannel, Sandor Nagy, Barbara Kimmich and Shannon S. Stahl*,
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引用次数: 0
摘要
二氧化碳与烯烃的还原偶联是合成羧酸的一种有效策略。本研究表明,Ni(OAc)2 和 6,6′-Me2bpy(dmbpy)可催化末端未活化烯烃的羧化反应,生成支链 2-甲基取代羧酸。通过电化学、紫外-可见光和核磁共振光谱方法,阐明了溶液中镍/dmbpy 的规格。确定了催化剂失活过程,其中涉及 CO2 竞争性还原为 CO,形成无活性的 Ni-CO 复合物。镍催化剂可以通过氧化处理镍-CO 复合物来重新激活,从而释放出 CO;然而,研究结果突显了镍催化与 CO2 的还原偶联反应中可能出现的一个重要的复杂问题。
Nickel-Catalyzed Hydrocarboxylation of Terminal Unactivated Alkenes: Formation of Branched Carboxylic Acids and Competing Catalyst Deactivation from CO2 Reduction to CO
The reductive coupling of CO2 and alkenes represents a compelling strategy for the synthesis of carboxylic acids. In this study, we show that Ni(OAc)2 and 6,6′-Me2bpy (dmbpy) catalyze hydrocarboxylation of terminal unactivated alkenes to afford the branched 2-methyl-substituted carboxylic acids. The nickel/dmbpy speciation in solution is elucidated through electrochemical and UV–visible and NMR spectroscopic methods. A catalyst deactivation process is identified, involving competitive reduction of CO2 to CO resulting in the formation of an inactive Ni–CO complex. The Ni catalyst may be reactivated by oxidative treatment of the Ni–CO complex to release CO; however, the results highlight an important complication that can arise in reactions of Ni-catalyzed reductive coupling with CO2.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.