Suzuki cross-coupling reaction catalyzed by sulfur-containing palladacycles: Formation of palladium active species

The construction of a high stability heterogeneous catalyst for privileged common catalysis is a benefit in regard to reuse and separation. Herein, a palladium diphenylphosphine-based hollow-shell-structured mesoporous catalyst (HS@PdPPh2@MSN) was prepared by immobilizing bis((diphenylphosphino)ethyltriethoxysilane)palladium acetate onto the inner wall of a mesoporous organicsilicane hollow shell, whose surface was protected by a –Si(Me)3 group. Electron microscopies confirmed its hollow-shell-structure, and structural analyses and characterizations revealed its well-defined single-site active species within the silicate network. As presented in this study, the newly constructed HS@PdPPh2@MSN enabled an efficient Suzuki-Miyaura cross-coupling reaction for varieties of substrates with up to 95% yield in mild conditions. Meanwhile, it could be reused at least five times with good activity, indicating its excellent stability and recyclability. Furthermore, the cost-effective and easily synthesized HS@PdPPh2@MSN made it a good candidate for employment in fine chemical engineering.

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Sulfur-Containing Palladacycles: Efficient Phosphine-Free Catalyst Precursors for the Suzuki Cross-Coupling Reaction at Room Temperature

Organic Letters ◽

10.1021/ol0063048 ◽

2000 ◽

Vol 2 (18) ◽

pp. 2881-2884 ◽

Cited By ~ 172

Author(s):

Danilo Zim ◽

Adriane S. Gruber ◽

Gunter Ebeling ◽

Jairton Dupont ◽

Adriano L. Monteiro

Keyword(s):

Room Temperature ◽

Coupling Reaction ◽

Cross Coupling ◽

Cross Coupling Reaction ◽

Sulfur Containing

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Nature of the Copper-Oxide-Mediated C–S Cross-Coupling Reaction: Leaching of Catalytically Active Species from the Metal Oxide Surface

ACS Catalysis ◽

10.1021/acscatal.6b00337 ◽

2016 ◽

Vol 6 (6) ◽

pp. 3637-3643 ◽

Cited By ~ 28

Author(s):

Yulia S. Panova ◽

Alexey S. Kashin ◽

Maxim G. Vorobev ◽

Evgeniya S. Degtyareva ◽

Valentine P. Ananikov

Keyword(s):

Metal Oxide ◽

Copper Oxide ◽

Coupling Reaction ◽

Cross Coupling ◽

Active Species ◽

Oxide Surface ◽

Metal Oxide Surface ◽

Cross Coupling Reaction ◽

Catalytically Active

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Metallic palladium, PdO, and palladium supported on metal oxides for the Suzuki–Miyaura cross-coupling reaction: a unified view of the process of formation of the catalytically active species in solution

Catalysis Science & Technology ◽

10.1039/c7cy01201b ◽

2017 ◽

Vol 7 (18) ◽

pp. 3934-3951 ◽

Cited By ~ 47

Author(s):

Alessandro Del Zotto ◽

Daniele Zuccaccia

Keyword(s):

Metal Oxide ◽

Metal Oxides ◽

Coupling Reaction ◽

Cross Coupling ◽

Active Species ◽

Cross Coupling Reaction ◽

Metallic Palladium ◽

Catalytically Active ◽

Unified View ◽

Supported Pd

The nature of the true catalytic species in the Suzuki–Miyaura coupling starting from metallic palladium, PdO, and metal oxide-supported Pd is critically reviewed.

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Ferromagnetic Chain Based on Verdazyl-Nitroxide Diradical

10.26434/chemrxiv.12367334.v1 ◽

2020 ◽

Author(s):

Evgeny Tretyakov ◽

Svetlana Zhivetyeva ◽

Pavel Petunin ◽

Dmitry Gorbunov ◽

Nina Gritsan ◽

...

Keyword(s):

Coupling Reaction ◽

Cross Coupling ◽

Ferromagnetic Coupling ◽

Nitronyl Nitroxide ◽

Triplet Ground State ◽

One Dimensional ◽

Cross Coupling Reaction ◽

Palladium Catalyzed ◽

Ferromagnetic Chain ◽

High Yields

Verdazyl-nitroxide diradicals were synthesized using the palladium-catalyzed cross-coupling reaction of the corresponding iodoverdazyls with a nitronyl nitroxide-2-ide gold(I) complex with high yields (up to 82%). The synthesized diradicals were found to be highly thermally stable and have a singlet (DEST » -64 cm–1) or triplet ground state (DEST ³ 25 and 100 cm–1), depending on which canonical hydrocarbon diradical type they belong to. Upon crystallization, triplet diradicals form unique one-dimensional (1D) spin S = 1 chains of organic diradicals with intrachain ferromagnetic coupling of J′/kB from 3 to 6 K.

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An Iron-Based Catalyst Enables The Enantioconvergent Synthesis of Chiral 1,1-Diarylalkanes Through a Suzuki-Miyaura Cross-Coupling Reaction

10.26434/chemrxiv.12582284.v1 ◽

2020 ◽

Author(s):

Chet Tyrol ◽

Nang Yone ◽

Connor Gallin ◽

Jeffery Byers

Keyword(s):

Coupling Reaction ◽

Cross Coupling ◽

Coupling Reactions ◽

Radical Intermediates ◽

Cross Coupling Reactions ◽

Cross Coupling Reaction ◽

Boronic Esters ◽

Carbon Centered Radical ◽

Iron Based ◽

High Yields

By using an iron-based catalyst, access to enantioenriched 1,1-diarylakanes was enabled through an enantioselective Suzuki-Miyaura crosscoupling reaction. The combination of a chiral cyanobis(oxazoline) ligand framework and 1,3,5-trimethoxybenzene additive were essential to afford high yields and enantioselectivities in cross-coupling reactions between unactivated aryl boronic esters and a variety of benzylic chlorides, including challenging ortho-substituted benzylic chloride substrates. Mechanistic investigations implicate a stereoconvergent pathway involving carbon-centered radical intermediates.

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Ni(0)-Catalyzed α-Allylic Alkylation of Regular Ketones with 1,3-Dienes under pH and Redox-neutral Conditions

10.26434/chemrxiv.7072646.v3 ◽

2019 ◽

Cited By ~ 1

Author(s):

Tiantian Chen ◽

Yang Yang ◽

Liyu Xie ◽

Haijian Yang ◽

Guangbin Dong ◽

...

Keyword(s):

Oxidative Addition ◽

Coupling Reaction ◽

Cross Coupling ◽

Dual Role ◽

Allylic Alkylation ◽

Cross Coupling Reaction ◽

Neutral Conditions

We report a Ni(0)-catalyzed cross coupling reaction between simple ketones and 1,3-dienes. A variety of a-allylic alkylation products were formed in an 1,2-addition manner with excellent regioselectivity. Water was found to significantly accelerate this transformation. A HO-Ni-H species generated from oxidative addition of Ni(0) to H2O is proposed to play a “dual role” in activating both the ketone and the diene substrate.

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