Orthopalladated phosphinite complexes as high-activity catalysts for the Suzuki reaction

Bedford, Robin B.; Hazelwood, Samantha L.; Horton, Peter N.; Hursthouse, Michael B.

doi:10.1039/b303657j

Cited by 116 publications

(62 citation statements)

References 28 publications

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“…More importantly, electron-rich analogues like 5b and 5c were shown to produce TONs > 10 6 for the coupling of deactivated aryl bromides with phenylboronic acid, and TONs > 10 8 for the same reaction with activated aryl bromides, in the presence of extra phosphite ligand. [100,101] A very important mechanistic observation was reported recently, also by Bedford et al, who reported that catalyst longevity for 5a -c increases appreciably in the presence of added phosphanes. For example, 5a -c plus added tri(cyclohexyl)phosphane (PCy 3 ) afford the largest TONs ever reported for the cross-coupling of deactivated aryl bromides, and allow even the coupling of deactivated aryl chlorides with excellent TON (Scheme 9).…”

Section: Vittorio Farina ð3þmentioning

confidence: 79%

High‐Turnover Palladium Catalysts in Cross‐Coupling and Heck Chemistry: A Critical Overview

2004

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This review discusses the problems associated with developing high-turnover catalysts for the cross-coupling and Heck reactions. New developments in the area, principally constituted by palladacycles and coordinatively unsaturated Pd catalysts featuring bulky phosphanes of high donicity, are reviewed from a mechanistic and synthetic standpoint, and compared with more traditional catalysts obtained from conventional mono-and polydentate Nand P-based ligands, as well as Pd catalysts without strong ligands, such as Pd colloids or heterogeneous catalysts. Carbene ligands are also briefly presented. Whereas a single, most promising approach to highturnover Pd catalysis cannot presently be defined, it is clear that the new "PdL 1 " catalysts (where L 1 is a monodentate bulky P ligand of high donicity) represent the latest, most important development in Pd research, certainly from the standpoint of scope and probably also from the standpoint of efficiency. High turnovers with these catalysts have been described and their use will certainly increase in the next few years. The review ends with a brief discussion containing practical considerations on how to choose a high TON catalyst for a given Heck or cross-coupling reaction of interest.

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Section: Vittorio Farina ð3þmentioning

confidence: 79%

High‐Turnover Palladium Catalysts in Cross‐Coupling and Heck Chemistry: A Critical Overview

2004

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“…Finally, the iron-catalyzed analogs of Pd-catalyzed crossScheme 7 Impact of impurities in an iron catalyst on an N-arylation reaction (top) [91] and coppercocatalyzed example (bottom) [93] coupling reactions might actually also be Pd catalyzed, as iron could contain palladium impurities. It has been shown that ppb quantities of Pd impurities can catalyze cross-coupling chemistry [100][101][102]. For example, a palladium-free, ironcatalyzed Suzuki reaction presented by Franzén [103] was later shown to be not reproducible [104], and the original paper has subsequently been retracted.…”

Section: Enantioselective Iron Catalysis and Stoichiometric Consideramentioning

confidence: 97%

Iron Catalysis: Historic Overview and Current Trends

Bauer

2015

Topics in Organometallic Chemistry

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Iron catalysis is a growing area of research, as seen by an exponential increase in the publication activities on the topic. This introductory chapter provides a historic overview of the development of iron catalysis including some notable milestones. The advantages of iron, i.e., its abundance, low price, and relative nontoxicity, are discussed, and an overview of the main type of reactions catalyzed by iron is outlined. The advances of heterogeneous iron catalysis (which is not covered in this volume) are exemplified with a few notable cases. Finally, the potential impact of metal impurities in iron sources on the catalytic activity is discussed.

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“…[20] Orthopalladated phosphinite complexes have also been employed for this coupling. [21,22] The influence of several solvents, bases and ligands has been studied. The best results were obtained with K 3 PO 4 in dioxane in the presence of P(OC 6 H 3 -2,4-tBu 2 ) 3 (0.5 mol-%) as ligand and Pd(OAc) 2 (0.5 mol-%).…”

Section: Methodsmentioning

confidence: 99%

Suzuki–Miyaura Cross‐Coupling Reactions of Alkylboronic Acid Derivatives or Alkyltrifluoroborates with Aryl, Alkenyl or Alkyl Halides and Triflates

2008

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Palladium‐catalysed Suzuki–Miyaura cross‐couplings of organoboronic acids or organotrifluoroborates with aryl and alkenyl halides or triflates have become classic methods for generating carbon–carbon bonds. For this reaction, not only sp2‐hybridized but also sp3‐hybridized organoboron derivatives can be employed. However, alkylboronic acids or trifluoroborates are generally less reactive than arylboron derivatives. The coupling of primary alkylboronic acids or alkyltrifluoroborates with aryl or alkenyl halides is well known, and the reaction gives the coupling products with high selectivities, relatively high turnover numbers and in good yields with several catalysts. On the other hand, secondary alkylboronic acids or trifluoroborates, except for cyclopropylboron derivatives, are much less reactive, and very few catalyst are able to activate such compounds. Because of the hybridization of cyclopropanes, which confers significant aromatic character, several reactions have successfully been performed with cyclopropylboronic acids or trifluoroborates. The stereochemistries of substituted cyclopropylboron derivatives were maintained in the course of the reactions. For all these couplings with primary or secondary alkylboron derivatives, aryl iodides, bromides, chlorides or triflates and alkenyl iodides, bromides or triflates were employed. Alkenyl chlorides have attracted less attention. The reactions with alkenyl halides are stereoselective. A few examples of couplings between sp3‐hybridized organoboronic acids and alkyl halides have also been reported.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Orthopalladated phosphinite complexes as high-activity catalysts for the Suzuki reaction

Cited by 116 publications

References 28 publications

High‐Turnover Palladium Catalysts in Cross‐Coupling and Heck Chemistry: A Critical Overview

High‐Turnover Palladium Catalysts in Cross‐Coupling and Heck Chemistry: A Critical Overview

Iron Catalysis: Historic Overview and Current Trends

Suzuki–Miyaura Cross‐Coupling Reactions of Alkylboronic Acid Derivatives or Alkyltrifluoroborates with Aryl, Alkenyl or Alkyl Halides and Triflates

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