Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan.
Chem Rev. 2021 Jan 13;121(1):264-299. doi: 10.1021/acs.chemrev.0c00569. Epub 2020 Sep 23.
This article reviews synthetic transformations involving cleavage of a carbon-carbon bond of a four-membered ring, with a particular focus on the examples reported during the period from 2011 to the end of 2019. Most significant is the progress of catalytic reactions involving oxidative addition of carbon-carbon bonds onto transition metals or β-carbon elimination of transition metal alkoxides. When they are looked at from synthetic perspectives, they offer unique and efficient methods to build complex natural products and structures that are difficult to construct by conventional methods. On the other hand, β-scission of radical intermediates has also attracted increasing attention as an alternative elementary step to cleave carbon-carbon bonds. Its site-selectivity is often complementary to that of transition metal-catalyzed reactions. In addition, Lewis acid-mediated and thermally induced ring-opening of cyclobutanone derivatives has garnered renewed attention. On the whole, these examples demonstrate unique synthetic potentials of structurally strained four-membered ring compounds for the construction of organic skeletons.
本文综述了涉及四元环碳-碳键断裂的合成转化，特别关注了 2011 年至 2019 年底期间报道的实例。其中最重要的是涉及碳-碳键向过渡金属的氧化加成或过渡金属烷氧基的β-碳消除的催化反应的进展。从合成的角度来看，它们为构建复杂的天然产物和结构提供了独特而有效的方法，这些产物和结构通常难以用传统方法构建。另一方面，自由基中间体的β-断裂作为一种替代的断碳-碳键的基本步骤也引起了越来越多的关注。其位点选择性通常与过渡金属催化反应互补。此外，Lewis 酸介导和热诱导的环丁酮衍生物的开环反应也重新引起了人们的关注。总的来说，这些实例展示了结构应变的四元环化合物在构建有机骨架方面的独特合成潜力。
