Chemoselective Intramolecular Formal Insertion Reaction of Rh–Nitrenes into an Amide Bond Over C−H Insertion

Kono, Masato; Harada, Shingo; Nemoto, Tetsuhiro

doi:10.1002/chem.201805878

Cited by 35 publications

(12 citation statements)

References 82 publications

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“… Dirhodium(II,II) complexes containing O , O ‘‐bridging ligands with structural motive OOC‐spacer‐COO: W1 , [250] W2 , [251] W3 , [252] W4 , [253] W5 , [254] W6 , [252] W7a R=H, [255] W7b R= t Bu, [256] W8 , [257] W9 , [188] W10 , [258] W11 , [258] W12 , [71] W13 [259] …”

Section: Overview Of Rh2a4 Paddlewheel Complexesmentioning

confidence: 99%

Dirhodium(II,II) Paddlewheel Complexes

Hrdina

2021

Eur J Inorg Chem

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This minireview summarizes synthetic approaches towards homoleptic dirhodium(II,II) paddlewheel complexes with the general formula Rh2A4. These complexes have found numerous applications in a wide range of chemical research and industry as catalysts, detectors, enzymatic inhibitors or building blocks for molecular scaffolds. In organic synthesis they are commonly used to transfer electron‐deficient species, they act as Lewis acids to activate unsaturated bonds, serve as hydrogenation catalysts and participate in oxidation/reduction processes. Dirhodium paddlewheel complexes are composed of the Rh‐Rh backbone and four bridging anions, which surround the core. According to the application, the electrochemical potential of the Rh atom can be modulated, as can the geometry and physical and chemical properties of the metal complex. Dirhodium complexes can be prepared in one step from basic inorganic precursors or by post‐functionalization of the paddlewheel structures.

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Section: Overview Of Rh2a4 Paddlewheel Complexesmentioning

confidence: 99%

Dirhodium(II,II) Paddlewheel Complexes

Hrdina

2021

Eur J Inorg Chem

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“…The process begins with an ylide formation by the coordination of a suitably located lactam to the metallonitrene, followed by the migration of the acyl group to the nitrogen. The authors identified that an electronically optimized Rh 2 (esp) 2 catalyst selectively formed 35 through the ylide formation ( Scheme 11 a ), [49] whereas a silver complex ligated by an achiral BOX ligand yielded C−H amination product 36 ( Scheme 11 b ) [50] …”

Section: Intramolecular Nitrene Transfersmentioning

confidence: 99%

Catalyst‐Controlled Chemoselective Nitrene Transfers

Noda

Tang

Shibasaki

2021

Helvetica Chimica Acta

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Transition metal catalyzed nitrene transfers provide nitrogen containing compounds through C−H bond insertion, aziridination of olefins, and other types of reactions. Given the importance of these compounds in natural products and pharmaceuticals, tremendous efforts have been devoted to the development of efficient and reliable catalytic methods. In particular, the last decade has seen a remarkable progress in catalyst‐controlled chemoselective nitrene transfers, wherein different products can be obtained from a single substrate by the choice of catalyst. This Minireview covers this important and emerging area. We explain the principle of catalyst‐controlled synthesis, followed by highlighting literature examples for intra‐ and intermolecular reactions with an emphasis on the understanding of the nature of reactive intermediates and the strategy needed to realize selectivity. Finally, future directions are discussed based on the literature precedents.

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“…In our continuing research toward discovering unknown reactivities of metal–nitrene species, we reported nitrene insertion reactions into an amide C–N bond using an electronically tuned Rh(II) dimer complex . The amide insertion reaction proceeds through the generation of a Rh-associated N + – N – ylide with amide functionality, , followed by [1,2]-acyl transfer, which is thermodynamically disfavored yet kinetically preferred to the competing C–H insertion process.…”

Section: Introductionmentioning

confidence: 99%

Site-Selective and Chemoselective C–H Functionalization for the Synthesis of Spiroaminals via a Silver-Catalyzed Nitrene Transfer Reaction

et al. 2020

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Although intense research over the last 2 decades revealed a diverse proficiency of nitrene species in chemistry disciplines, control of the selectivity in the reaction manifold has remained a challenge. We report herein the development of siteselective and chemoselective C−H functionalization involving nitrene species to synthesize densely functionalized spiroaminals. A rhodium catalyst generally used in nitrene chemistry gave amide C−N insertion products and/or the corresponding ketones, whereas a silver catalyst with an achiral bisoxazoline (BOX) ligand provided C−H insertion products. Mechanistic analysis based on integrated experimental and computational studies indicated that the nitrene transfer occurred through an asynchronous concerted process involving triplet spin-correlated radical pairs, affording the corresponding stereodefined spiromolecules.

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Chemoselective Intramolecular Formal Insertion Reaction of Rh–Nitrenes into an Amide Bond Over C−H Insertion

Cited by 35 publications

References 82 publications

Dirhodium(II,II) Paddlewheel Complexes

Dirhodium(II,II) Paddlewheel Complexes

Catalyst‐Controlled Chemoselective Nitrene Transfers

Site-Selective and Chemoselective C–H Functionalization for the Synthesis of Spiroaminals via a Silver-Catalyzed Nitrene Transfer Reaction

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