Tri-tert-butyl(n-alkyl)phosphonium Ionic Liquids: Structure, Properties and Application as Hybrid Catalyst Nanomaterials

A series of sterically hindered tri-tert-butyl(n-alkyl)phosphonium salts (n-CnH2n+1 with n = 1, 3, 5, 7, 9, 11, 13, 15, 17) was synthesized and systematically studied by 1H, 13C, 31P NMR spectroscopy, ESI-MS, single-crystal X-ray diffraction analysis and melting point measurement. Formation and stabilization palladium nanoparticles (PdNPs) were used to characterize the phosphonium ionic liquid (PIL) nanoscale interaction ability. The colloidal Pd in the PIL systems was described with TEM and DLS analyses and applied in the Suzuki cross-coupling reaction. The PILs were proven to be suitable stabilizers of PdNPs possessing high catalytic activity. The tri-tert-butyl(n-alkyl)phosphonium salts showed a complex nonlinear correlation of the structure–property relationship. The synthesized family of PILs has a broad variety of structural features, including hydrophobic and hydrophilic structures that are entirely expressed in the diversity of their properties

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Room-Temperature, Water-Promoted, Radical-Coupling Reactions of Phenols with tert-Butyl Nitrite

Synlett ◽

10.1055/s-0036-1589038 ◽

2017 ◽

Vol 28 (16) ◽

pp. 2153-2156 ◽

Cited By ~ 13

Author(s):

Wen-Ting Wei ◽

Hongze Liang ◽

Wen-Ming Zhu ◽

Weida Liang ◽

Yi Wu ◽

...

Keyword(s):

Room Temperature ◽

Coupling Reaction ◽

Cross Coupling ◽

Coupling Reactions ◽

Phenol Derivative ◽

Tert Butyl ◽

Radical Coupling ◽

Air Atmosphere ◽

Cross Coupling Reaction ◽

Temperature Water

A radical–radical cross-coupling reaction of phenols with tert-butyl nitrite has been developed with the use of water as an additive. This method allows the construction of C–N bonds under an air atmosphere at room temperature, providing the ortho-nitrated phenol derivative in moderate to good yields.

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Electrochemical Synthesis of 2-Hydroxy-para-terphenyls by Dehydrogenative Anodic C–C Cross-Coupling Reaction

Synlett ◽

10.1055/s-0037-1611942 ◽

2019 ◽

Vol 30 (10) ◽

pp. 1174-1177 ◽

Cited By ~ 7

Author(s):

Sebastian Lips ◽

Robert Franke ◽

Siegfried R. Waldvogel

Keyword(s):

Functional Groups ◽

Electrochemical Synthesis ◽

Coupling Reaction ◽

Cross Coupling ◽

Cross Coupling Reaction ◽

Wide Range ◽

Broad Variety ◽

First Time ◽

Fast Access

The anodic C–C cross-coupling reaction provides fast access to a wide range of bi- and terarylic scaffolds by electrochemically mediated arylation reactions. Herein, a metal- and reagent-free electrosynthetic protocol for the synthesis of nonsymmetrical 2-hydroxy-para-teraryl derivatives is presented for the first time. It is scalable, easy to conduct, and allows the use of a broad variety of different functional groups.

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N,N-Dimethylformamide-stabilized copper nanoparticles as a catalyst precursor for Sonogashira–Hagihara cross coupling

RSC Advances ◽

10.1039/c6ra27910d ◽

2017 ◽

Vol 7 (37) ◽

pp. 22869-22874 ◽

Cited By ~ 12

Author(s):

Hideo Oka ◽

Katsuya Kitai ◽

Takeyuki Suzuki ◽

Yasushi Obora

Keyword(s):

Catalytic Activity ◽

Copper Nanoparticles ◽

Coupling Reaction ◽

Cross Coupling ◽

High Catalytic Activity ◽

Catalyst Precursor ◽

Cross Coupling Reaction

We found that DMF-stabilized Cu NPs have high catalytic activity in the Sonogashira cross-coupling reaction at low catalyst loadings (0.2 mol%).

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Structural features influencing the activity of bis-biguanide ligands in the Suzuki–Miyaura cross-coupling reaction in neat water

Canadian Journal of Chemistry ◽

10.1139/cjc-2020-0033 ◽

2020 ◽

Vol 98 (9) ◽

pp. 547-553

Author(s):

Solène Fortun ◽

Philippe Beauclair ◽

Andreea R. Schmitzer

Keyword(s):

Catalytic Activity ◽

Green Chemistry ◽

Coupling Reaction ◽

Cross Coupling ◽

Structural Features ◽

Catalytic Reactions ◽

Neat Water ◽

Cross Coupling Reaction ◽

Integral Role ◽

Reaction In Water

Catalytic reactions play an integral role in the development of green chemistry. Herein, we report new bis-biguanide compounds containing alkyl and aryl spacers as ligands for the Suzuki–Miyaura cross-coupling reaction in water. These ligands show similar catalytic activity to metformin independently of the nature of the spacer between the two biguanide units.

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SCREENING OF THE CATALYTIC ACTIVITY OF Pd0 AND Pd2+- SUPPORTED ON CHITOSAN BEADS AND CRYOGELS

Progress on Chemistry and application of Chitin and its Derivatives ◽

10.15259/pcacd.23.015 ◽

2018 ◽

Vol XXIII ◽

pp. 149-158

Author(s):

Aleksandr Pestov ◽

Aleksandr Mekhaev ◽

Yuliya Privar ◽

Natalya Prokuda ◽

Evgeniy Modin ◽

...

Keyword(s):

Catalytic Activity ◽

Coupling Reaction ◽

Cross Coupling ◽

Pd Nanoparticles ◽

High Catalytic Activity ◽

Mesomeric Effect ◽

Catalytic Systems ◽

Chitosan Beads ◽

Cross Coupling Reaction ◽

Significant Difference

Here, we report the results of screening of the catalytic activity of Pd-containing chitosan beads and cryogels in the cross-coupling reaction, hydrogenation of alkenes, nitro-, and carbonyl compounds and the hydrodechlorination of chlorophenols. Pd0-containing chitosan beads and cryogels show moderate catalytic activity in the reduction of alkenes and nitroaromatics. The conversion of nitroaromatics decreases for substrates with electron-withdrawing substituents, while the conversion of alkenes increases with the activation of carbon-carbon double bonds. For several substrates, a significant difference in kinetics and conversion degrees was observed for Pd nanoparticles supported on chitosan beads and cryogels. It was found that conversion in the hydrodechlorination reaction depends on substrate structure, being higher for substrates containing substituents with a positive mesomeric effect. Pd2+-chitosan catalysts showed high catalytic activity in cross-coupling (Heck reaction) offering the following advantages over known catalytic systems: lower reaction temperature, the selective functionalisation of C-I bonds, and the possibility to perform reactions with iodobenzene without base addition.

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Mono- and Bimetallic Nanoparticles Stabilized by an Aromatic Polymeric Network for a Suzuki Cross-Coupling Reaction

Nanomaterials ◽

10.3390/nano12010094 ◽

2021 ◽

Vol 12 (1) ◽

pp. 94

Author(s):

Linda Zh. Nikoshvili ◽

Kristina N. Shkerina ◽

Alexey V. Bykov ◽

Alexander I. Sidorov ◽

Alexander L. Vasiliev ◽

...

Keyword(s):

Bimetallic Nanoparticles ◽

Phenylboronic Acid ◽

Coupling Reaction ◽

Cross Coupling ◽

High Catalytic Activity ◽

Zno Nps ◽

Catalyst Recycling ◽

Catalyst Composition ◽

Water Solvent ◽

Cross Coupling Reaction

This work addresses the Suzuki cross-coupling between 4-bromoanisole (BrAn) and phenylboronic acid (PBA) in an environmentally benign ethanol–water solvent catalysed by mono- (Pd) and bimetallic (PdAu, PdCu, PdZn) nanoparticles (NPs) stabilised within hyper-cross-linked polystyrene (HPS) bearing tertiary amino groups. Small Pd NPs of about 2 nm in diameters were formed and stabilized by HPS independently in the presence of other metals. High catalytic activity and complete conversion of BrAn was attained at low Pd loading. Introduction of Zn to the catalyst composition resulted in the formation of Pd/Zn/ZnO NPs, which demonstrated nearly double activity as compared to Pd/HPS. Bimetallic core-shell PdAu/HPS samples were 3-fold more active as compared to Pd/HPS. Both Pd/HPS and PdAu/HPS samples revealed promising stability confirmed by catalyst recycling in repeated reaction runs.

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Sterically Hindered Phosphonium Salts: Structure, Properties and Palladium Nanoparticle Stabilization

Nanomaterials ◽

10.3390/nano10122457 ◽

2020 ◽

Vol 10 (12) ◽

pp. 2457

Author(s):

Daria M. Arkhipova ◽

Vadim V. Ermolaev ◽

Vasily A. Miluykov ◽

Aidar T. Gubaidullin ◽

Daut R. Islamov ◽

...

Keyword(s):

Palladium Nanoparticles ◽

Coupling Reaction ◽

Phosphonium Salts ◽

New Family ◽

Cross Coupling Reaction ◽

Catalytically Active ◽

Nanoparticle Stabilization ◽

Sterically Hindered ◽

Exceptional Stability ◽

Structure Properties

A new family of sterically hindered alkyl(tri-tert-butyl) phosphonium salts (n-CnH2n+1 with n = 2, 4, 6, 8, 10, 12, 14, 16, 18, 20) was synthesized and evaluated as stabilizers for the formation of palladium nanoparticles (PdNPs), and the prepared PdNPs, stabilized by a series of phosphonium salts, were applied as catalysts of the Suzuki cross-coupling reaction. All investigated phosphonium salts were found to be excellent stabilizers of metal nanoparticles of small catalytically active size with a narrow size distribution. In addition, palladium nanoparticles exhibited exceptional stability: the presence of phosphonium salts prevented agglomeration and precipitation during the catalytic reaction.

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Synthesis and Structure of (Nitronyl Nitroxide-2-ido)(tert-butyldiphenylphosphine)gold(I) and -(Di(tert-butyl)phenylphosphine)gold(I) Derivatives; Their Comparative Study in the Cross-Coupling Reaction

Crystals ◽

10.3390/cryst10090770 ◽

2020 ◽

Vol 10 (9) ◽

pp. 770

Author(s):

Igor Zayakin ◽

Irina Bagryanskaya ◽

Dmitri Stass ◽

Maxim Kazantsev ◽

Evgeny Tretyakov

Keyword(s):

Coupling Reaction ◽

Cross Coupling ◽

Oxidation Potential ◽

Nitronyl Nitroxide ◽

X Ray ◽

Tert Butyl ◽

Cross Coupling Reaction ◽

Vis Spectroscopy ◽

The Cross ◽

Derivatives Of

We synthesized two new organogold derivatives of a nitronyl nitroxide (NN) with phosphine ligands, namely NN-Au-PtBuPh2 and NN-Au-PtBu2Ph. They were characterized by X-ray diffraction analysis, cyclic voltammetry, and ESR, IR, and UV/Vis spectroscopy. The X-ray structural analysis revealed a tendency of the NN moiety to form a large number of short intermolecular contacts. This phenomenon is related to the anionic nature of the paramagnetic group NN, as evidenced by a significantly lower oxidation potential in comparison with purely organic derivatives of NN radicals. The cross-coupling reaction of NN-Au-PPh3, NN-Au-PtBuPh2, or NN-Au-PtBu2Ph with an activated bromoarene, namely, p-BrC6H4NO2, was investigated. It was shown that regardless of the presence of the bulky tert-butyl substituent, all gold derivatives have similar activities in the cross-coupling reaction and give a cross-coupling product, NN-C6H4NO2, with comparable yields.

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Synthesis of Mono- and Bis-Pyrazoles Bearing Flexible p-Tolyl Ether and Rigid Xanthene Backbones, and Their Potential as Ligands in the Pd-Catalysed Suzuki–Miyaura Cross-Coupling Reaction

Catalysts ◽

10.3390/catal9090718 ◽

2019 ◽

Vol 9 (9) ◽

pp. 718

Author(s):

Zahid Hussain ◽

Cristiane Schwalm ◽

Raoní Rambo ◽

Renieidy Dias ◽

Rafael Stieler ◽

...

Keyword(s):

Catalytic System ◽

Good Yield ◽

Coupling Reaction ◽

Cross Coupling ◽

Boronic Acids ◽

Aryl Halides ◽

Tert Butyl ◽

Cross Coupling Reaction ◽

Ullmann Coupling

The present work describes the synthesis of mono- and bis-pyrazole compounds bearing flexible p-tolyl ether and rigid 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene backbones as pyrazolyl analogues of DPEphos and Xantphos ligands, respectively. The synthesis of new pyrazolyl analogues was accomplished following an Ullmann coupling protocol, and the resulting products were isolated in overall good yields. In addition, a hybrid imidazolyl–pyrazolyl analogue bearing a xanthene backbone was synthesized using the same protocol, whereas a hybrid selanyl–pyrazolyl analogue with a xanthene backbone was synthesized in a good yield employing a second C–H activation step. The symmetrical bis-pyrazolyl and the hybrid imidazolyl–pyrazolyl analogues were found to be the most active among the new ligands evaluated in the Pd-catalysed Suzuki-Miyaura cross-coupling of aryl halides with aryl boronic acids. A simple catalytic system based on Pd(OAc)2/2a was developed, which efficiently catalyses the Suzuki–Miyaura reaction of aryl halides and aryl boronic acids and provides moderate to excellent yields of the corresponding cross-coupling products.

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