Room Temperature Ruthenium-Catalyzed Coupling of Cyclopropanols and α-Diazo-β-Ketoesters to α-Ester-δ-Diketones

Organic synthesis in the conventional descriptor wisdom of reactivity chemistry scheme asserts functional group as the originator of reactivity in reactive site, leading to ill-informed reaction development from a static, local perspective. We report herein the proposal of reactivity transduction chemistry scheme, a descriptor system highlighting reactivity and reactive fragment flow as the source for emergence of reactivity, showcasing a well-informed, dynamic, global perspective for reaction development. Through the lens of this descriptor system, the reactivity flow of zinc carbenoid and azide promises the differentiation of ineffective ketone–β-ketoester cross coupling reactivity into competent cyclopropanol–α-diazo carbene cross coupling reactivity. Correspondingly, a room temperature ruthenium catalytic protocol has been developed for the coupling of cyclopropanols and α-diazo-β-ketoesters to α-ester-δ-diketones, featuring a broad substrate scope. The two-carbonyl, one-ester molecular architecture in α-ester-δ-diketones presents an ideal combinatorial synthetic handle for further elaboration into a diversified pool of linear and cyclic structures. The ubiquity of reactivity flow in reaction chains promises reactivity transduction chemistry as a powerful conceptual tool for the productive establishment of most efficient global reactivity network.