Rhodium(II)‐Catalyzed Nondirected Oxidative Alkenylation of Arenes: Arene Loading at One Equivalent

Vora, Harit U.; Silvestri, Anthony P.; Engelin, Casper J.; Yu, Jin‐Quan

doi:10.1002/ange.201310539

Cited by 56 publications

(5 citation statements)

References 62 publications

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“…This challenge is illustrated by the very limited reports on transition-metal-catalyzed C-H functionalization with arene as the limiting reagent. [43][44][45][46][47][48][49][50][51] In 2017, Yu and coworkers reported a palladium (Pd)catalyzed, pyridone-ligand-enabled Fujiwara-Moritani olefination reaction with arenes as limiting reagent. 43 Shortly thereafter, van Gemmeren reported the same transformation using a combination of a pyridine ligand and a mono-N-protected amino acid (MPAA) ligand.…”

Section: The Bigger Picturementioning

confidence: 99%

Palladium-Catalyzed Late-Stage Direct Arene Cyanation

Zhao

Ritter

2019

Chem

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Section: The Bigger Picturementioning

confidence: 99%

Palladium-Catalyzed Late-Stage Direct Arene Cyanation

Zhao

Ritter

2019

Chem

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“…As aresult of these studies,avariety of synthetic methods mostly based on Ir-a nd Rh-catalysis has been reported, which have proven particularly useful for late-stage C À heteroatom bond formation. [5,6] In contrast, Pd-catalysis has remained underdeveloped and until recently no general methods were available that allowed for the arene-limited nondirected formation of arylpalladium species.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of the Arene‐Limited Nondirected C−H Activation of Arenes with Palladium**

et al. 2021

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Recently palladium catalysts have been discovered that enable the directing-group-free CÀHa ctivation of arenes without requiring an excess of the arene substrate,t hereby enabling methods for the late-stage modification of complex organic molecules.The key to success has been the use of two complementary ligands,a nN -acyl amino acid and an Nheterocycle.D etailed experimental and computational mechanistic studies on the dual-ligand-enabled CÀHa ctivation of arenes have led us to identify the catalytically active species and at ransition state model that explains the exceptional activity and selectivity of these catalysts.These findings are expected to be highly useful for further method development using this powerful class of catalysts.

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“…Such mononuclear rhodium complexes have been proposed as plausible intermediates in the whole catalytic cycle, although their re-dimerization has not been considered . However, when weak bulky monodentate ligands are used in the reaction, monomerization is unlikely to occur because of the insufficient coordination of the rhodium center by the ligands owing to strong repulsion …”

Section: Introductionmentioning

confidence: 99%

Synergistic Dinuclear Rhodium Induced Rhodium-Walking Enabling Alkene Terminal Arylation: A Theoretical Study

Heng

Chen

et al. 2021

ACS Catal.

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Dinuclear transition-metal catalysis is a distinctive approach for cross-coupling reactions, but Rh(I)–Rh(III) redox catalysis has rarely been considered. Here, a dinuclear Rh(III)–Rh(III) redox catalytic cycle for [Rh(coe)2Cl]2-catalyzed remote terminal arylation of activated olefins is proposed and validated by density functional theory. Calculations reveal that the catalytic cycle of terminal arylation involves phosphine-directed oxidative addition of the indole C7(aryl)–H bond, alkene insertion, Rh-walking, and reductive elimination. Throughout the catalytic cycle, the dinuclear rhodium complex remains intact, and each of the rhodium atoms have important roles. One acts as the active catalytic center and undergoes Rh(I)–Rh(III) redox cycles; the other remains in the +3 oxidation state after the pre-catalytic cycle and is not directly involved in the reactions but affects the chemoselectivity by adjusting the coordination environment of the active rhodium atom. The hydroarylation regioselectivity is controlled by steric effects, which distinguish different reactive sites in the dinuclear rhodium pathway. The mononuclear rhodium catalytic cycle is unfavorable because of the endothermic monomerization process. A tether effect in the reductive elimination step also restricts generation of the δ-arylation product in the mononuclear pathway.

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Rhodium(II)‐Catalyzed Nondirected Oxidative Alkenylation of Arenes: Arene Loading at One Equivalent

Cited by 56 publications

References 62 publications

Palladium-Catalyzed Late-Stage Direct Arene Cyanation

Palladium-Catalyzed Late-Stage Direct Arene Cyanation

Mechanism of the Arene‐Limited Nondirected C−H Activation of Arenes with Palladium**

Synergistic Dinuclear Rhodium Induced Rhodium-Walking Enabling Alkene Terminal Arylation: A Theoretical Study

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