Transition-metal-catalyzed aromatic C–H functionalization assisted by the phosphorus-containing directing groups

Zhang, Jian; Yao, Lingyun; Su, Jiong-Guang; Liu, Yang‐Zi; Wang, Quannan; Deng, Wei‐Ping

doi:10.1016/j.gresc.2023.02.001

Cited by 9 publications

(2 citation statements)

References 126 publications

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“…[11][12][13] This concept of Functional Group Transfer Reagents (FGTRs) [14] has enabled access to unprecedentedly mild conditions for the release of radical species, and thus expended the chemical space through their broader utilization in synthetic organic chemistry. Selective and regulated production of the desired radical by activation of an appropriate FGTR can be carried out by photoredox catalysis, [15][16][17][18][19][20][21][22] irradiation of Electron Donor-Acceptor (EDA) complexes, [23,24] electrochemistry, [25][26][27][28][29] electro-photocatalysis, [30,31] the use of semiconductor materials, [32][33][34] metal catalysis [35][36][37][38] and other activation modes (Figure 1B).…”

Section: Introductionmentioning

confidence: 99%

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Fernandes,

Giri,

Houk

et al. 2024

Angewandte Chemie

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We highlight key contributions in the field of direct radical CAr–H (hetero)aromatic functionalization involving fluorinated radicals. A compilation of Functional Group Transfer Reagents and their diverse activation mechanisms leading to the release of radicals are discussed. The substrate scope for each radical is analyzed and classified into three categories according to the electronic properties of the substrates. Density functional theory computational analysis provides insights into the chemical reactivity of several fluorinated radicals through their electrophilicity and nucleophilicity parameters. Theoretical analysis of their reduction potentials also highlights the remarkable correlation between electrophilicity and oxidizing ability. It is also established that highly fluorinated radicals (e.g.•OCF3) are capable of engaging in single‐electron transfer (SET) processes rather than radical addition, which is in good agreement with experimental literature data. A reactivity scale, based on activation barrier of addition of these radicals to benzene is also elaborated using the high accuracy DLPNO‐(U)CCSD(T) method.

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Section: Introductionmentioning

confidence: 99%

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Fernandes,

Giri,

Houk

et al. 2024

Angewandte Chemie

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“…The C-7 functionalized indoles and indolines are important structural scaffolds and are found in many natural alkaloids, biologically active compounds, pharmaceutical molecules, and functional materials (Figure ). With the development of transition-metal-catalyzed C–H bond activation, chemists have spent a great deal of effort to develop methods for the direct C-7 functionalization of indoles and indolines, which is more challenging than direct C-2 and C-3 functionalization of indoles . In particular, the direct C-7 arylation of indoles is very challenging (Scheme a) .…”

Section: Introductionmentioning

confidence: 99%

Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions

Gao

Zhang

et al. 2023

J. Org. Chem.

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A palladium-catalyzed direct C−H arylation of indolines at C-7 position has been achieved at near-ambient temperature. The reaction was carried out with aryltriazene as a stable aryl source and electron shuttle to sustainably release aryl radical in situ under the action of promoter, and pyrimidine as a detachable directing group for the synthesis of 7-arylindolines under oxidant-and ligand-free conditions. Notably, this catalytic system can also be applied to the direct and site-selective arylation of tetrahydroquinolines (C-8) and carbazoles (C-1).

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Merging Visible Light Photocatalysis and P(III)‐Directed C−H Activation by a Single Catalyst: Modular Assembly of P‐Alkyne Hybrid Ligands

Jiang,

Yang,

Lin

et al. 2023

Angewandte Chemie

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Metal‐catalyzed C−H activation strategies provide an efficient approach for synthesis by minimizing atom, step, and redox economy. Developing milder, greener, and more effective protocols for these strategies is always highly desirable to the scientific community. In this study, the utilization of a single rhodium complex enabled the visible‐light‐induced late‐stage C−H activation of biaryl‐type phosphines with alkynyl bromides, employing inherent phosphorus atoms as directing groups. This chemistry combines P(III)‐directed C−H activation with visible light photocatalysis, under exogenous photosensitizer‐free conditions, offering a unique platform for ligand design and preparation. Furthermore, this study also explores the asymmetric catalysis and coordination chemistry of the resulting P‐alkyne hybrid ligands with specific transition metals. Experimental results and density functional theory calculations demonstrate the mechanistic intricacies of this transformation.

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Transition-metal-catalyzed aromatic C–H functionalization assisted by the phosphorus-containing directing groups

Cited by 9 publications

References 126 publications

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions

Merging Visible Light Photocatalysis and P(III)‐Directed C−H Activation by a Single Catalyst: Modular Assembly of P‐Alkyne Hybrid Ligands

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Transition-metal-catalyzed aromatic C–H functionalization assisted by the phosphorus-containing directing groups

Cited by 9 publications

References 126 publications

Review and Theoretical Analysis of Fluorinated Radicals in Direct CAr−H Functionalization of (Hetero)arenes

Review and Theoretical Analysis of Fluorinated Radicals in Direct CAr−H Functionalization of (Hetero)arenes

Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions

Merging Visible Light Photocatalysis and P(III)‐Directed C−H Activation by a Single Catalyst: Modular Assembly of P‐Alkyne Hybrid Ligands

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Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes