Perspective on dirhodium carboxamidates as catalysts.
TL;DR: With chiral carboxamidate ligands these dirhodium compounds show exceptional enantiocontrol for intramolecular cyclopropanation and carbon-hydrogen insertion reactions of diazoacetates, and they are also highly efficient and selective for hetero-Diels-Alder reactions.
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Abstract: Dirhodium compounds are emerging as highly efficient catalysts for diverse reactions, and those with carboxamidate ligands have the broadest applications. The unique features of these compounds are their structural rigidity, ease of ligand exchange, open diaxial sites for coordination with Lewis bases, and their low oxidation potential. As consequences of this, dirhodium carboxamidates are efficient and effective catalysts for metal carbene reactions, Lewis acid-catalyzed processes, and chemical oxidations. With chiral carboxamidate ligands these dirhodium compounds show exceptional enantiocontrol for intramolecular cyclopropanation and carbon-hydrogen insertion reactions of diazoacetates, and they are also highly efficient and selective for hetero-Diels-Alder reactions. Their limitations lie in their moderate reactivities for metal carbene generation and Lewis acid catalysis and in the cost of the precious metal rhodium.
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Citations
Elucidating the Electronic Nature of Rh-basedPaddlewheel Catalysts from 103Rh NMRChemical Shifts: Insights from QuantumMechanical Calculations.
Xin Gui,Diego Sorbelli,Fabio P. Caló,Markus Leutzsch,Michael Patzer,Alois Fürstner,Giovanni Bistoni,Alexander Auer +7 more
TL;DR: The electronic structure of Rh-based paddlewheel catalysts is influenced by the ligand sphere geometry and electronic properties. The shielding of the Rh-site is dominated by the donor ability of the equatorial ligands, while axial ligands exert an electronic cis-effect. Charge redistribution within the core and the electronic trans-effect of ligands are also reflected in the 103Rh NMR shifts.
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Electrochemical Oxidative Difunctionalization of Diazo Compounds with Diselenides and Nucleophiles.
TL;DR: Electrochemical oxidative difunctionalization of diazo compounds with diselenides and nucleophiles yields selenium-containing pyrazole esters and alkoxy esters with high atom efficiency, excellent functional group tolerance, and good efficiency under transition metal- and oxidant-free conditions.
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Synthesis and Characterization of Rhodium Acetate with Functionalized Benzonitriles
Jared M Lowe
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TL;DR: In this article, a large amount of the adduct was dissolved into water and tested the solution's acidity, with a pH decrease indicating that water did abstract the hydrogen atom, and the results showed that the acidity of water did not indicate that the hydrogen was removed.
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Deconvoluting Nonlinear Catalyst–Substrate Effects in the Intramolecular Dirhodium-Catalyzed C–H Insertion of Donor/Donor Carbenes Using Data Science Tools
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TL;DR: Deconvoluting nonlinear catalyst–substrate effects in the intramolecular dirhodium-catalyzed C–H insertion of donor/donor carbenes using data science tools leads to a high-performing model that predicts external validation points well and provides mechanistic insights into the reaction.
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