Catalyst-Controlled Aliphatic C–H Oxidations with a Predictive Model for Site-Selectivity

Selective aliphatic C-H bond oxidations may have a profound impact on synthesis because these bonds exist across all classes of organic molecules. Central to this goal are catalysts with broad substrate scope (small-molecule-like) that predictably enhance or overturn the substrate’s inherent reactivity preference for oxidation (enzyme-like). We report a simple small-molecule, non-heme iron catalyst that achieves predictable catalyst-controlled site-selectivity in preparative yields over a range of topologically diverse substrates. A catalyst reactivity model quantitatively correlates the innate physical properties of the substrate to the site-selectivities observed as a function of the catalyst

Catalyst-Controlled Aliphatic C–H Oxidations with a Predictive Model for Site-Selectivity

Selective aliphatic C-H bond oxidations may have a profound impact on synthesis because these bonds exist across all classes of organic molecules. Central to this goal are catalysts with broad substrate scope (small-molecule-like) that predictably enhance or overturn the substrate’s inherent reactivity preference for oxidation (enzyme-like). We report a simple small-molecule, non-heme iron catalyst that achieves predictable catalyst-controlled site-selectivity in preparative yields over a range of topologically diverse substrates. A catalyst reactivity model quantitatively correlates the innate physical properties of the substrate to the site-selectivities observed as a function of the catalyst

Catalyst-Controlled Aliphatic C–H Oxidations with a Predictive Model for Site-Selectivity

Selective aliphatic C-H bond oxidations may have a profound impact on synthesis because these bonds exist across all classes of organic molecules. Central to this goal are catalysts with broad substrate scope (small-molecule-like) that predictably enhance or overturn the substrate’s inherent reactivity preference for oxidation (enzyme-like). We report a simple small-molecule, non-heme iron catalyst that achieves predictable catalyst-controlled site-selectivity in preparative yields over a range of topologically diverse substrates. A catalyst reactivity model quantitatively correlates the innate physical properties of the substrate to the site-selectivities observed as a function of the catalyst

Oxidative Heck Vinylation for the Synthesis of Complex Dienes and Polyenes

We introduce an oxidative Heck reaction for selective complex diene and polyene formation. The reaction proceeds via oxidative Pd­(II)/sulfoxide catalysis that retards palladium-hydride isomerizations which previously limited the Heck manifold’s capacity for furnishing stereodefined conjugated dienes. Limiting quantities of nonactivated terminal olefins (1 equiv) and slight excesses of vinyl boronic esters (1.5 equiv) that feature diverse functionality can be used to furnish complex dienes and polyenes in good yields and excellent selectivities (generally <i>E</i>:<i>Z</i> = >20:1; internal:terminal = >20:1). Because this reaction only requires prior activation of a single vinylic carbon, improvements in efficiency are observed for synthetic sequences relative to ones featuring reactions that require activation of both coupling partners