Palladium-Catalyzed Benzene Arylation:  Incorporation of Catalytic Pivalic Acid as a Proton Shuttle and a Key Element in Catalyst Design

Lafrance, Marc; Fagnou, Keith

doi:10.1021/ja067144j

Cited by 954 publications

(512 citation statements)

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“…However, 1,2,3-triazoles with two n-alkyl-substituents reacted rather sluggishly under our reaction conditions. Here, a significant rate-acceleration was accomplished with catalytic amounts of pivalic acid [29][30][31] as additive (entries 4 and 5). With respect to the electrophile, electron-rich aryl chlorides could generally be employed (entries 1-5), even when being more sterically hindered through ortho-substitution (entry 6).…”

Section: Resultsmentioning

confidence: 99%

Palladium‐Catalyzed Direct Arylations of 1,2,3‐Triazoles with Aryl Chlorides using Conventional Heating

2008

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Section: Resultsmentioning

confidence: 99%

Palladium‐Catalyzed Direct Arylations of 1,2,3‐Triazoles with Aryl Chlorides using Conventional Heating

2008

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“…45,46 Fagnou first used pivalic acid (PivOH) as a co-catalyst in a palladium-catalyzed direct arylation reaction in order to efficiently functionalize benzene and other simple arenes. 47 The pivalate anion is believed to act as a catalytic proton shuttle from benzene to the stoichiometric carbonate base. Without this additive, very little conversion of starting material to product was obtained.…”

Section: ç Additives Used To Enhance Reactivitymentioning

confidence: 99%

Overview of the Mechanistic Work on the Concerted Metallation–Deprotonation Pathway

2010

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The cleavage of aromatic CH bonds promoted by a metal and an intramolecular base has been described over 50 years ago. Herein, discussion of selected mechanistic studies of this transformation will be presented. The basic ligand on the metal was proven to play a pivotal role in the CH bond cleavage step and evidence of a single operative concerted metallation deprotonation mechanism unifies the different mechanistic studies.

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“…While many noble metals have proven to be quite effective to cleave inactivated Csp2-H and Csp3-H bonds, one of the most recognized catalytic system for the functionalization of C-H bonds is the direct arylation pioneered by Fagnou and coworkers [86][87][88][89]. The key feature of this catalytic transformation is the C-H activation of an arene by a palladium pivalate complex [86].…”

Section: C-h Borylation Of Heteroarenes: a Proof Of Conceptmentioning

confidence: 99%

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

Fontaine

Courtemanche

Légaré

et al. 2017

Coordination Chemistry Reviews

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This is the peer reviewed version of the following article: [Design Principles in Frustrated Lewis KeywordsFrustrated Lewis pairs, Ambiphilic molecules, Boron, Aluminum, Carbon dioxide, Methanol, C-H activation. Highlights 1.Phosphine-aluminum frustrated Lewis pairs (FLPs) can activate CO2 but show significant stability issues. 2.The Lewis acidity and basicity need to be fine-tuned to the desired reactivity for efficient FLP catalysis.3. FLP catalysts need to generate strong hydrides to reduce catalytically carbon dioxide. 4.Transition metal catalysis can serve as an inspiration for the design of metal-free catalysts for many transformations, including the borylation of heteroarenes. Graphical abstract AbstractThis account describes our work on the use of ambiphilic molecules as catalysts for the reduction of carbon dioxide. Starting with the discovery that aluminum ambiphilic species (Me2PCH2AlMe2)2 (1) and Al(C6H4-PPh3)3 (5) could coordinate CO2 but showed significant instability, we found that phosphinoborane Ph2P-2-Bcat-C6H4 (7) was an exceptional catalyst for the hydroboration of CO2 to methoxyboranes, a molecule that can be readily hydrolyzed to methanol. A mechanistic investigation allowed us to outline the similarities between the catalytic activity of frustrated Lewis pairs (FLPs) and that of transition metal complexes. We were able to extrapolate four important guidelines, described in this account, to synthesize efficient metal-free catalysts. We demonstrate that using these concepts it was possible to rationally design FLP catalysts for the C-H borylation of heteroarenes.

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Palladium-Catalyzed Benzene Arylation: Incorporation of Catalytic Pivalic Acid as a Proton Shuttle and a Key Element in Catalyst Design

Cited by 954 publications

References 12 publications

Palladium‐Catalyzed Direct Arylations of 1,2,3‐Triazoles with Aryl Chlorides using Conventional Heating

Palladium‐Catalyzed Direct Arylations of 1,2,3‐Triazoles with Aryl Chlorides using Conventional Heating

Overview of the Mechanistic Work on the Concerted Metallation–Deprotonation Pathway

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

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