Suzuki–Miyaura and Hiyama coupling catalyzed by PEPPSI-type complexes with non-bulky NHC ligand

Osińska, M; Gniewek, Andrzej; Trzeciak, Anna M.

doi:10.1016/j.molcata.2016.03.022

Cited by 40 publications

(25 citation statements)

References 38 publications

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“…The possible reason for this reactivity could be the relatively strong connection between ethylene glycol and Pd, which prevents CO access . Thus, under carbonylative Suzuki–Miyaura conditions, the activation of CO was not efficient as a result of the blocking of the Pd environment by ethylene glycol or by products of its dehydrogenation …”

Section: Resultssupporting

confidence: 79%

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Carbonylative Suzuki Coupling Reaction Catalyzed by a Hydrospirophosphorane Palladium Complex

et al. 2017

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Section: Resultssupporting

confidence: 79%

“…The ability of ethylene glycol to promote Suzuki–Miyaura coupling has been observed for other Pd complexes and is because ethylene glycol facilitates the reduction of Pd II to Pd 0 . Similarly, if Cat.…”

Section: Resultsmentioning

confidence: 99%

Carbonylative Suzuki Coupling Reaction Catalyzed by a Hydrospirophosphorane Palladium Complex

et al. 2017

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“…PEPPSI-themed complexes are well-defined, user-friendly, easily-prepared, and air-and moisture-stable Pd II precatalysts utilized in palladium-catalyzed C-C and C-N bond-forming reactions (Valente et al, 2012;Nun et al, 2009;Martínez-Olid et al, 2015;Huang et al, 2012;Zhang et al, 2015;Wang et al, 2015;Yig it et al, 2011). In addition, they have remarkable activities with respect to many challenging reactions, such as Suzuki-Miyaura, Negishi, Kumada-Tamao-Corriu coupling, Buchwald-Hartwig-Yagupol'skii amination (Organ et al, 2008), Stille-Migita (Cordovilla et al, 2015), Mizoroki-Heck (Aktaş et al, 2013), Sonogashira (Dehimat et al, 2018), Hiyama coupling (Osiń ska et al, 2016) and direct arylation (Akkoç et al, 2016;Kalog lu et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

Enhanced π-back-donation resulting in thetranslabilization of a pyridine ligand in an N-heterocyclic carbene (NHC) Pd^IIprecatalyst: a case study

et al. 2019

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The molecular structure of the benzimidazol‐2‐ylidene–PdCl2–pyridine‐type PEPPSI (pyridine‐enhanced precatalyst, preparation, stabilization and initiation) complex {1,3‐bis[2‐(diisopropylamino)ethyl]benzimidazol‐2‐ylidene‐κC2}dichlorido(pyridine‐κN)palladium(II), [PdCl2(C5H5N)(C23H40N4)], has been characterized by elemental analysis, IR and NMR spectroscopy, and natural bond orbital (NBO) and charge decomposition analysis (CDA). Cambridge Structural Database (CSD) searches were used to understand the structural characteristics of the PEPPSI complexes in comparison with the usual N‐heterocyclic carbene (NHC) complexes. The presence of weak C—H…Cl‐type hydrogen‐bond and π–π stacking interactions between benzene rings were verified using NCI plots and Hirshfeld surface analysis. The preferred method in the CDA of PEPPSI complexes is to separate their geometries into only two fragments, i.e. the bulky NHC ligand and the remaining fragment. In this study, the geometry of the PEPPSI complex is separated into five fragments, namely benzimidazol‐2‐ylidene (Bimy), two chlorides, pyridine (Py) and the PdII ion. Thus, the individual roles of the Pd atom and the Py ligand in the donation and back‐donation mechanisms have been clearly revealed. The NHC ligand in the PEPPSI complex in this study acts as a strong σ‐donor with a considerable amount of π‐back‐donation from Pd to Ccarbene. The electron‐poor character of PdII is supported by π‐back‐donation from the Pd centre and the weakness of the Pd—N(Py) bond. According to CSD searches, Bimy ligands in PEPPSI complexes have a stronger σ‐donating ability than imidazol‐2‐ylidene ligands in PEPPSI complexes.

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“…In the majority of studies, it is thought that the introduction of bulky ligands in the skeleton of Pd‐NHC complexes is a strong strategy. Also, Pd‐NHC complexes have been proven to be very effective in C−C (such as Suzuki‐Miyaura, Mizoroki‐Heck, Negishi, Sonogashira, Stille, Kumada‐Corriu, Hiyama and Direct arylation reaction) and C‐heteroatom (such as Animation) bond formation reactions.…”

Section: Introductionmentioning

confidence: 99%

2‐Hydroxyethyl‐Substituted Pd‐PEPPSI Complexes: Synthesis, Characterization and the Catalytic Activity in the Suzuki‐Miyaura Reaction for Aryl Chlorides in Aqueous Media

et al. 2018

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In recent years, PEPPSI (Pyridine‐Enhanced Precatalyst Preparation Stabilization and Initiation) complexes have attracted attention in organometallic chemistry. This study contains the synthesis of the 2‐hydroxyethyl‐substituted Pd‐PEPPSI complexes and their catalytic activity in the Suzuki‐Miyaura reaction aryl chlorides in aqueous media. The Pd‐PEPPSI complexes have been prepared from the 2‐ hydroxyethyl‐substituted N‐heterocyclic carbene (NHC) precursors, palladium chloride and 3‐chloropyridine. The Pd‐PEPPSI complexes have been characterized by using 1H NMR, 13C NMR, FTIR spectroscopy and elemental analysis techniques. The Pd‐PEPPSI complexes have been examined as catalysts in the Suzuki‐Miyaura reactions in aqueous media with arylboronic acid derivatives. Also, they have demonstrated excellent activity in these reactions. Molecular and crystal structure of one of the 2‐hydroxyethyl substituted Pd‐PEPPSI complex was determined by single crystal X‐ray diffraction method. X‐ray studies show that the molecular structure adopts a slightly distorted square‐planar geometry with the palladium (II) center.

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Suzuki–Miyaura and Hiyama coupling catalyzed by PEPPSI-type complexes with non-bulky NHC ligand

Cited by 40 publications

References 38 publications

Carbonylative Suzuki Coupling Reaction Catalyzed by a Hydrospirophosphorane Palladium Complex

Carbonylative Suzuki Coupling Reaction Catalyzed by a Hydrospirophosphorane Palladium Complex

Enhanced π-back-donation resulting in thetranslabilization of a pyridine ligand in an N-heterocyclic carbene (NHC) Pd^IIprecatalyst: a case study

2‐Hydroxyethyl‐Substituted Pd‐PEPPSI Complexes: Synthesis, Characterization and the Catalytic Activity in the Suzuki‐Miyaura Reaction for Aryl Chlorides in Aqueous Media

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Suzuki–Miyaura and Hiyama coupling catalyzed by PEPPSI-type complexes with non-bulky NHC ligand

Cited by 40 publications

References 38 publications

Carbonylative Suzuki Coupling Reaction Catalyzed by a Hydrospirophosphorane Palladium Complex

Carbonylative Suzuki Coupling Reaction Catalyzed by a Hydrospirophosphorane Palladium Complex

Enhanced π-back-donation resulting in thetranslabilization of a pyridine ligand in an N-heterocyclic carbene (NHC) PdIIprecatalyst: a case study

2‐Hydroxyethyl‐Substituted Pd‐PEPPSI Complexes: Synthesis, Characterization and the Catalytic Activity in the Suzuki‐Miyaura Reaction for Aryl Chlorides in Aqueous Media

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Enhanced π-back-donation resulting in thetranslabilization of a pyridine ligand in an N-heterocyclic carbene (NHC) Pd^IIprecatalyst: a case study