Key role of a π–π complex in diaryl cross-coupling between aryldiazonium salts and arylboronic acids using photosensitizer-free gold/photoredox catalysis

Liu, Yanhong; Zhu, Rongxiu; Liu, Chengbu; Zhang, Dongju

doi:10.1039/d1qo01464a

Cited by 7 publications

(1 citation statement)

References 63 publications

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“…The coordination of a1 to the Pd–dppp complex by the phosphonyl oxygen and the coordination of c1 to the Pd–dppp complex are less stable (Scheme S2). From 2 , P–H oxidative addition occurs via TS1 with nearly no energy barrier to form planar square Pd(II) complex 3 , showing that this step is feasible. Then alkyne b1 recoordinates to the Pd(II) center along with which one Pd–P bond becomes loosened and shifts to the axial position, generating a formal tetragonal pyramidal complex 4 .…”

Section: Resultsmentioning

confidence: 99%

Computational Study Revealing the Mechanistic Origin of Distinct Performances of P(O)–H/OH Compounds in Palladium-Catalyzed Hydrophosphorylation of Terminal Alkynes: Switchable Mechanisms and Potential Side Reactions

et al. 2022

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Pd-catalyzed hydrophosphorylation of alkynes with P(O)−H compounds provided atom-economical and oxidant-free access to alkenylphosphoryl compounds. Nevertheless, the applicable P(O)−H substrates were limited to those without a hydroxyl group except H 2 P(O)OH. It is also puzzling that Ph 2 P(O)OH could co-catalyze the reaction to improve Markovnikov selectivity. Herein, a computational study was conducted to elucidate the mechanistic origin of the phenomena described above. It was found that switchable mechanisms influenced by the acidity of substrates and co-catalysts operate in hydrophosphorylation. In addition, potential side reactions caused by the protonation of Pd II −alkenyl intermediates with P(O)−OH species were revealed. The regeneration of an active Pd(0) catalyst from the resulting Pd(II) complexes is remarkably slower than the hydrophosphonylation, while the downstream reactions, if possible, would lead to phosphorus 2pyrone. Further analysis indicated that the side reactions could be suppressed by utilizing bulky substrates or ligands or by decreasing the concentration of P(O)−OH species. The presented switchable mechanisms and side reactions shed light on the cotransformations of P(O)−H and P−OH compounds in the Pd-catalyzed hydrophosphorylation of alkynes, clarify the origin of the distinct performances of P(O)−H/OH compounds, and provide theoretical clues for expanding the applicable substrate scope of hydrophosphorylation and synthesizing cyclic alkenylphosphoryl compounds.

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Section: Resultsmentioning

confidence: 99%

Computational Study Revealing the Mechanistic Origin of Distinct Performances of P(O)–H/OH Compounds in Palladium-Catalyzed Hydrophosphorylation of Terminal Alkynes: Switchable Mechanisms and Potential Side Reactions

et al. 2022

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Oxy‐ and Chloroarylation Pathways in Gold‐Mediated Cyclization of 2‐Aminoaryl‐3‐arylpropargyl‐benzenesulfonamides

Díaz‐Salazar,

Medina‐Mercado,

Salvador‐Reyes

et al. 2023

Chemistry A European J

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We described herein a one‐pot diazotization/gold‐mediated cyclization of 2‐aminoaryl‐3‐arylpropargyl‐benzenesulfonamides. After diazotization, Me2SAuCl triggers an oxy‐ and/or chloroarylation of the alkyne moiety, resulting in the formation of 3‐acylindoles and/or Z‐3‐(chloromethylene)indolines. Density Functional Theory (DFT) calculations show the significant energetic preference of both processes over an insertion pathway. Notably, a Z‐3‐(chloromethylene)indoline crystallized with [Cl‐Au‐Cl],‐ exhibiting Au⋅⋅⋅H‐C short contacts.

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Computational Understanding of Dual Gold and Photoredox-Catalyzed Regioselective Thiosulfonylation of Alkenes

Wang

Bao

2023

J. Org. Chem.

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Herein, a computational work was carried out to gain mechanistic insights into dual gold and photoredox-catalyzed regioselective thiosulfonylation of alkenes with PhSO 2 SCF 3 . Computational results suggest that it is more favorable for the complex of Au(I) with PhSO 2 SCF 3 (INT1), instead of an Au(I) catalyst or individual substrates, to quench the excited *[Ru] II photocatalyst in a single-electron oxidative manner to afford [Ru] III . The complexation of the Au(I) catalyst with PhSO 2 SCF 3 could lead to a substantially lowered energy level of the lowest unoccupied molecular orbital, which may be mainly responsible for the feasibility of INT1 in quenching the excited photocatalyst. The resultant single-electron reduced complex, subsequently, is ready to undergo a S−S bond cleavage to form an Au(I)−SCF 3 species and a benzenesulfonyl radical. Next, the yielded Au(I)−SCF 3 species could undergo single-electron oxidation by [Ru] III to afford an Au(II) intermediate. Subsequently, the binding with an alkyl radical for the formed Au(II) species could occur to further convert to an Au(III) species, from which the final product can be furnished by a reductive elimination step and the Au(I) catalyst is regenerated. Thus, an Au(I)/Au(II)/Au(III)/Au(I) catalytic cycle is suggested to mainly account for the regioselective thiosulfonylation of alkenes.

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Key role of a π–π complex in diaryl cross-coupling between aryldiazonium salts and arylboronic acids using photosensitizer-free gold/photoredox catalysis

Abstract: In a new mechanism for photosensitizer-free visible-light-mediated gold-catalyzed cross-coupling, the π–π complex between aryldiazonium salts and arylboronic acids acts as a photoinitiator.

Cited by 7 publications

References 63 publications

Computational Study Revealing the Mechanistic Origin of Distinct Performances of P(O)–H/OH Compounds in Palladium-Catalyzed Hydrophosphorylation of Terminal Alkynes: Switchable Mechanisms and Potential Side Reactions

Computational Study Revealing the Mechanistic Origin of Distinct Performances of P(O)–H/OH Compounds in Palladium-Catalyzed Hydrophosphorylation of Terminal Alkynes: Switchable Mechanisms and Potential Side Reactions

Oxy‐ and Chloroarylation Pathways in Gold‐Mediated Cyclization of 2‐Aminoaryl‐3‐arylpropargyl‐benzenesulfonamides

Computational Understanding of Dual Gold and Photoredox-Catalyzed Regioselective Thiosulfonylation of Alkenes

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