Kinetics of Rh(II)-Catalyzed α-Diazo-β-ketoester Decomposition and Application to the [3+6+3+6] Synthesis of Macrocycles on a Large Scale and at Low Catalyst Loadings

Citations Over TimeTop 10% of 2016 papers

Abstract

In the context of [3+6+3+6] macrocyclization reactions, precise kinetics of α-diazo-β-ketoester decomposition were measured by in situ infrared (IR) monitoring. Dirhodium complexes of Ikegami–Hashimoto type—and perchlorinated phthalimido derivatives in particular—performed better than classical achiral complexes. Clear correlations were found between speciation among dirhodium species and catalytic activity. With these results, novel cyclohexyl-derived catalysts were developed, affording good yields of macrocycles (up to 78%), at low catalyst loadings (from 0.01 mol % to 0.001 mol %) and on a large scale (from 1 g to 20 g).

Related Papers

• → Atomically dispersed rhodium on a support: the influence of a metal precursor and a support(2014)14 cited
• → Factors determining rhodium solubilization efficiency in molten K2CO3–K2O–B2O3–Al2O3 medium(2023)2 cited
• → The effect of rhodium precursor on Rh/Al2O3 catalysts(1982)54 cited
• → ChemInform Abstract: BASIC METALS. XI. CATIONIC (CYCLOPENTADIENYL)RHODIUM COMPLEXES CONTAINING RHODIUM‐HYDROGEN, RHODIUM‐CARBON, RHODIUM‐GERMANIUM, RHODIUM‐TIN, AND RHODIUM‐HALOGEN BONDS(1979)
• Progress in Rhodium Determination Method for Rhodium-containing Materials(2014)