Dimethyl Diazomalonate

Predictive Model for the [Rh2(esp)2]-Catalyzed Intermolecular C(sp3)–H Bond Insertion of β-Carbonyl Ester Carbenes: Interplay between Theory and Experiment

“…Diazo-derived metal-carbenes have been a cornucopia of synthetically useful reactivity. The reactivity of these species prominently features C–H and X–H bond activation, cyclopropanation, and a host of [3 + 2] cycloaddition chemistry. − Metal-carbene compounds have been subdivided between five categories: acceptor only (A), acceptor–acceptor (A–A), donor–acceptor (D–A), donor–donor (D–D), and donor only (D) (Figure ). To date, studies on D–A carbenoids feature a panoply of selective C­(sp 3 )–H functionalization chemistry in which the donor group is credited with stabilizing the metal-carbene interaction .…”

“…Therefore, this Article investigates the reactivity of dirhodium­(tetracarboxylate)-carbene complexes, derived from A–A diazo compounds, with alkane substrates in an aim to develop generalized predictive rules for their effective utilization in selective intermolecular C­(sp 3 )–H functionalization reactions. Previous investigations of intermolecular C­(sp 3 )–H functionalization reactions have focused solely on carbenes derived from dimethyl diazomalonate and thus similarly lack comprehensiveness. , As such, little is known on the influence of the nature of the acceptor groups on A–A carbene C­(sp 3 )–H insertion in an intermolecular dirhodium­(tetracarboxylate)-catalyzed manifold.…”