Catalytic Carbonyl-Olefin Metathesis of Aliphatic Ketones: Iron(III) Homo-Dimers as Lewis Acidic Superelectrophiles
作者:Haley Albright、Paul S. Riehl、Christopher C. McAtee、Jolene P. Reid、Jacob R. Ludwig、Lindsey A. Karp、Paul M. Zimmerman、Matthew S. Sigman、Corinna S. Schindler
DOI:10.1021/jacs.8b11840
日期:2019.1.30
carbon-carbon bond formation. However, currently available synthetic protocols rely exclusively on aryl ketone substrates while the corresponding aliphatic analogs remain elusive. We herein report the development of Lewis acid-catalyzed carbonyl-olefin ring-closing metathesis reactions for aliphatic ketones. Mechanistic investigations are consistent with a distinct mode of activation relying on the in
催化羰基-烯烃复分解反应最近已被开发为形成碳-碳键的有力工具。然而,目前可用的合成协议完全依赖于芳基酮底物,而相应的脂肪族类似物仍然难以捉摸。我们在此报告了路易斯酸催化的脂肪族酮羰基-烯烃闭环复分解反应的发展。机理研究与依赖于原位形成的均双金属单桥联铁 (III)-二聚体作为假定的活性催化物质的独特活化模式一致。这些“超亲电试剂”充当更强大的路易斯酸催化剂,在单个铁 (III) 单体结合后形成。虽然之前假设存在这种路易斯酸活化模式,它尚未应用于催化环境。所提出的见解有望通过建立在“超亲电试剂”的活化原理基础上,进一步推动路易斯酸催化的发展,并拓宽催化羰基-烯烃复分解反应的当前范围。