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
Enantioselective Synthesis of Aminodiols by Sequential Rhodium-Catalysed Oxyamination/Kinetic Resolution: Expanding the Substrate Scope of Amidine-Based Catalysis.
Joan Guasch,Irene Giménez‐Nueno,Ignacio Funes-Ardoiz,Miguel Bernús,M. Isabel Matheu,Feliu Maseras,Sergio Castillón,Yolanda Díaz +7 more
TL;DR: Regio- and stereoselective oxyamination of dienes through a tandem rhodium-catalysed aziridination-nucleophilic opening affords racemic oxazolidinone derivatives, which undergo a kinetic resolution acylation process with amidine-based catalysts (ABCs) to achieve s values of up to 117.
16
Dirhodium: Carbene Transformations and Beyond
Rui Wu,Dong Zhu,Shizheng Zhu +2 more
TL;DR: The dirhodiums, which feature lantern-or paddlewheel-like structures, have emerged as a class of useful catalysts in organic synthesis and have been shown to be useful in the transformation of carbene with the diazo transformation as mentioned in this paper .
16
Carboxylate lability as a factor in the Rh2(carboxylate)4-catalysed cyclopropenation and cyclopropanation of alkynes and alkenes.
TL;DR: Calculations show that both pathways in the mechanism of Rh(2)(carboxylate)(4)-catalysed cyclopropenation andcyclopropanation via two different pathways are equally favoured and the importance of coordinated solvent in determining the reaction pathway is demonstrated.
16
Rh(II)-Catalyzed Reactions of Diazoesters with Organozinc Reagents
TL;DR: Rh(II)-catalyzed reactions of diazoesters with organozinc reagents are described and a straightforward route to the hydrazone products provides a useful method for preparing chiral quaternary α-aminoesters or pyrazoles via the Paul-Knorr condensation with 1,3-diketones.
15
Assessing the Metal-Metal Interactions in a Series of Heterobimetallic Nb/M Complexes (M = Fe, Co, Ni, Cu) and Their Effect on Multielectron Redox Properties.
Brett A. Barden,Gursu Culcu,Jeremy P. Krogman,Mark W. Bezpalko,Gregory P. Hatzis,Diane A. Dickie,Bruce M. Foxman,Christine M. Thomas,Christine M. Thomas +8 more
TL;DR: A comparison of the cyclic voltammograms of 2 and 4-10 reveals that the presence of a second metal shifts the redox potentials of both Nb and the late metal center anodically, even when direct metal-metal interactions are not present.
15
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