<i>meta</i>‐Selective C−H Activation of Arenes at Room Temperature Using Visible Light: Dual‐Function Ruthenium Catalysis

Sagadevan, Arunachalam; Greaney, Michael F.

doi:10.1002/anie.201904288

Cited by 148 publications

(66 citation statements)

References 46 publications

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“…Visible‐light photoredox catalysis allowed for direct transformations at ambient temperature, however, additional iridium or ruthenium photocatalysts were required in these transformations among others as reported by MacMillan, Molander and Doyle. In contrast, Ackermann and Greaney recently disclosed photo‐induced ruthenium‐catalyzed remote C−H alkylations. After submission of the present manuscript, Greaney has reported on a ruthenium‐catalyzed arylation of phenylpyridines using visible light, which was proposed to occur by an oxidative addition/reductive elimination process .…”

Section: Introductionmentioning

confidence: 99%

“…Greaney [15] recently disclosed photo-induced ruthenium-catalyzed remote C À Ha lkylations.A fter submission of the present manuscript, Greaney has reported on ar utheniumcatalyzed arylation of phenylpyridines using visible light, which was proposed to occur by an oxidative addition/ reductive elimination process. [16] Within our program on sustainable CÀHa ctivation, [17] we have now devised the first light-driven ruthenium-catalyzed CÀHa rylations at ambient temperature (Figure 1c).…”

Section: Introductionmentioning

confidence: 99%

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Photo‐Induced Ruthenium‐Catalyzed C−H Arylations at Ambient Temperature

et al. 2020

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Ambient temperature ruthenium‐catalyzed C−H arylations were accomplished by visible light without additional photocatalysts. The robustness of the ruthenium‐catalyzed C−H functionalization protocol was reflected by a broad range of sensitive functional groups and synthetically useful pyrazoles, triazoles and sensitive nucleosides and nucleotides, as well as multifold C−H functionalizations. Biscyclometalated ruthenium complexes were identified as the key intermediates in the photoredox ruthenium catalysis by detailed computational and experimental mechanistic analysis. Calculations suggested that the in situ formed photoactive ruthenium species preferably underwent an inner‐sphere electron transfer.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Photo‐Induced Ruthenium‐Catalyzed C−H Arylations at Ambient Temperature

et al. 2020

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“…Grasping the essence of the mechanism of these systems one can intuitively conclude that the unique feature of photoredox catalysis is not the ability to facilitate any specific reaction but rather its capability to turn inactive substrates into reactive radical intermediates through high-energy intermolecular outer-sphere electron transfer. Consequently, the most typical application of TMPRCs includes the generation of, among many others, electrophilic α-carbonyl radicals [29], trifluoromethyl radicals [30], arene radical cations, iminium ions, and enone radical anions [31], of which these intermediates have been used to drive other types of transformations including atom transfer radical additions [32], arene C−H functionalizations [25,33,34], and amine α-functionalizations to [2 + 2] cycloadditions [35,36]. Cooperative catalysis, in which another transition metal co-catalyst is sensitized through electron transfer and its catalytic cycle is supported by the photoredox catalyst has been recently added to the arsenal of applications [37][38][39][40].…”

Section: Introductionmentioning

confidence: 99%

A DFT Study on the Redox Active Behavior of Carbene and Pyridine Ligands in the Oxidative and Reductive Quenching Cycles of Ruthenium Photoredox Catalysts

Medina

Pintér

2020

Catalysts

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In this study, a detailed look at the electronic structure changes induced by photon absorption and of the succeeding redox events of the oxidative and reductive quenching cycles of ruthenium–carbene and ruthenium–pyridine photoredox catalysts is provided through an arsenal of density functional theory-based techniques including electron density difference Δρ(r) maps, spin-density distributions, and the non-covalent interaction analysis. We introduced an efficient computational protocol to obtain accurate equilibrium structures and ground-state reduction potentials for these types of complexes, substantiated via a direct comparison to empirical X-ray structures and cyclic voltammetry measurements, respectively. Moreover, we demonstrated the utility of a hitherto unexplored approach to compute excited-state redox potentials based on the Gibbs free energy of the triplet metal-to-ligand charge transfer state (3MLCT). The analyzed Δρ(r) maps revealed the characteristic features of, for example, metal- and ligand-centered reductions and oxidations in both ground and excited states and MLCT processes, disclosing the active participation of carbene ligands in the redox events of homoleptic systems. Beyond analyzing ligand–ligand non-covalent interactions and redox-active behaviors of carbene and pyridine ligands side by side, the effect of such groups on the kinetics of 3MLCT to 3MC transition was scrutinized.

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“…The pioneering work in this extremely challenging research field was reported concomitantly by the groups of Ackermann [100] and Greaney [101], and concerned unique Ru-catalyzed meta-selective C-H alkylation of arenes. The ruthenium-catalyzed meta-selective C-H functionalization through arene σ-activation was already well established yet limited by harsh reaction conditions and elevated reaction temperatures.…”

Section: Direct Metalation and Visible-light Absorption By A Single Cmentioning

confidence: 99%

When metal-catalyzed C–H functionalization meets visible-light photocatalysis

Guillemard¹,

Wencel‐Delord²

2020

Beilstein J. Org. Chem.

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While aiming at sustainable organic synthesis, over the last decade particular attention has been focused on two modern fields, C–H bond activation, and visible-light-induced photocatalysis. Couplings through C–H bond activation involve the use of non-prefunctionalized substrates that are directly converted into more complex molecules, without the need of a previous functionalization, thus considerably reduce waste generation and a number of synthetic steps. In parallel, transformations involving photoredox catalysis promote radical reactions in the absence of radical initiators. They are conducted under particularly mild conditions while using the visible light as a cheap and economic energy source. In this way, these strategies follow the requirements of environment-friendly chemistry. Regarding intrinsic advantages as well as the complementary mode of action of the two catalytic transformations previously introduced, their merging in a synergistic dual catalytic system is extremely appealing. In that perspective, the scope of this review aims to present innovative reactions combining C–H activation and visible-light induced photocatalysis.

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meta‐Selective C−H Activation of Arenes at Room Temperature Using Visible Light: Dual‐Function Ruthenium Catalysis

Cited by 148 publications

References 46 publications

Photo‐Induced Ruthenium‐Catalyzed C−H Arylations at Ambient Temperature

Photo‐Induced Ruthenium‐Catalyzed C−H Arylations at Ambient Temperature

A DFT Study on the Redox Active Behavior of Carbene and Pyridine Ligands in the Oxidative and Reductive Quenching Cycles of Ruthenium Photoredox Catalysts

When metal-catalyzed C–H functionalization meets visible-light photocatalysis

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