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The Heck reaction is the chemical reaction of an unsaturated halide with an alkene in the presence of a base and a palladium catalyst to form a substituted alkene. It is named after Tsutomu Mizoroki and Richard F. Heck. Heck was awarded the 2010 Nobel Prize in Chemistry, which he shared with Ei-ichi Negishi and Akira Suzuki, for the discovery and development of this reaction. This reaction was the first example of a carbon-carbon bond-forming reaction that followed a Pd(0)/Pd(II) catalytic cycle, the same catalytic cycle that is seen in other Pd(0)-catalyzed cross-coupling reactions. The Heck reaction is a way to substitute alkenes.
The Suzuki reaction is an organic reaction, classified as a cross-coupling reaction, where the coupling partners are a boronic acid and an organohalide and the catalyst is a palladium(0) complex. It was first published in 1979 by Akira Suzuki, and he shared the 2010 Nobel Prize in Chemistry with Richard F. Heck and Ei-ichi Negishi for their contribution to the discovery and development of palladium-catalyzed cross-couplings in organic synthesis. This reaction is also known as the Suzuki–Miyaura reaction or simply as the Suzuki coupling. It is widely used to synthesize polyolefins, styrenes, and substituted biphenyls. Several reviews have been published describing advancements and the development of the Suzuki reaction. The general scheme for the Suzuki reaction is shown below, where a carbon-carbon single bond is formed by coupling a halide (R1-X) with an organoboron species (R2-BY2) using a palladium catalyst and a base. The organoboron species is usually synthesized by hydroboration or carboboration, allowing for rapid generation of molecular complexity.
The Sonogashira reaction is a cross-coupling reaction used in organic synthesis to form carbon–carbon bonds. It employs a palladium catalyst as well as copper co-catalyst to form a carbon–carbon bond between a terminal alkyne and an aryl or vinyl halide.
In chemistry, a transition metal pincer complex is a type of coordination complex with a pincer ligand. Pincer ligands are chelating agents that binds tightly to three adjacent coplanar sites in a meridional configuration. The inflexibility of the pincer-metal interaction confers high thermal stability to the resulting complexes. This stability is in part ascribed to the constrained geometry of the pincer, which inhibits cyclometallation of the organic substituents on the donor sites at each end. In the absence of this effect, cyclometallation is often a significant deactivation process for complexes, in particular limiting their ability to effect C-H bond activation. The organic substituents also define a hydrophobic pocket around the reactive coordination site. Stoichiometric and catalytic applications of pincer complexes have been studied at an accelerating pace since the mid-1970s. Most pincer ligands contain phosphines. Reactions of metal-pincer complexes are localized at three sites perpendicular to the plane of the pincer ligand, although in some cases one arm is hemi-labile and an additional coordination site is generated transiently. Early examples of pincer ligands were anionic with a carbanion as the central donor site and flanking phosphine donors; these compounds are referred to as PCP pincers.
The Hiyama coupling is a palladium-catalyzed cross-coupling reaction of organosilanes with organic halides used in organic chemistry to form carbon–carbon bonds. This reaction was discovered in 1988 by Tamejiro Hiyama and Yasuo Hatanaka as a method to form carbon-carbon bonds synthetically with chemo- and regioselectivity. The Hiyama coupling has been applied to the synthesis of various natural products.
The Negishi coupling is a widely employed transition metal catalyzed cross-coupling reaction. The reaction couples organic halides or triflates with organozinc compounds, forming carbon-carbon bonds (C-C) in the process. A palladium (0) species is generally utilized as the metal catalyst, though nickel is sometimes used. A variety of nickel catalysts in either Ni0 or NiII oxidation state can be employed in Negishi cross couplings such as Ni(PPh3)4, Ni(acac)2, Ni(COD)2 etc.
1,1′-Bis(diphenylphosphino)ferrocene, commonly abbreviated dppf, is an organophosphorus compound commonly used as a ligand in homogeneous catalysis. It contains a ferrocene moiety in its backbone, and is related to other bridged diphosphines such as 1,2-bis(diphenylphosphino)ethane (dppe).
In organic chemistry, the Kumada coupling is a type of cross coupling reaction, useful for generating carbon–carbon bonds by the reaction of a Grignard reagent and an organic halide. The procedure uses transition metal catalysts, typically nickel or palladium, to couple a combination of two alkyl, aryl or vinyl groups. The groups of Robert Corriu and Makoto Kumada reported the reaction independently in 1972.
In organic chemistry, a cross-coupling reaction is a reaction where two different fragments are joined. Cross-couplings are a subset of the more general coupling reactions. Often cross-coupling reactions require metal catalysts. One important reaction type is this:
CataCXium F sulf is a water-soluble organophosphorus compound derived from fluorene. The palladium complexes of the respective phosphine show an excellent activity in various palladium-catalyzed coupling reactions, including Suzuki reactions, Sonogashira couplings and Buchwald–Hartwig reactions.
Bis(triphenylphosphine)palladium chloride is a coordination compound of palladium containing two triphenylphosphine and two chloride ligands. It is a yellow solid that is soluble in some organic solvents. It is used for palladium-catalyzed coupling reactions, e.g. the Sonogashira–Hagihara reaction. The complex is square planar. Many analogous complexes are known with different phosphine ligands.
PEPPSI is an abbreviation for pyridine-enhanced precatalyst preparation stabilization and initiation. It refers to a family of commercially available palladium catalysts developed around 2005 by Prof. Michael G. Organ and co-workers at York University, which can accelerate various carbon-carbon and carbon-heteroatom bond forming cross-coupling reactions. In comparison to many alternative palladium catalysts, Pd-PEPPSI-type complexes are stable to air and moisture and are relatively easy to synthesize and handle.
A metal-phosphine complex is a coordination complex containing one or more phosphine ligands. Almost always, the phosphine is an organophosphine of the type R3P (R = alkyl, aryl). Metal phosphine complexes are useful in homogeneous catalysis. Prominent examples of metal phosphine complexes include Wilkinson's catalyst (Rh(PPh3)3Cl), Grubbs' catalyst, and tetrakis(triphenylphosphine)palladium(0).
John Perry Wolfe is an American chemist and a professor of chemistry at the University of Michigan. He is best known for palladium-catalyzed C-C and C-N bond formation reactions. He was also one of the key scientists in the development of Buchwald ligands, one of which is appropriately named "JohnPhos" after him. Wolfe has taught at the University of Michigan since 2002.
In organometallic chemistry, palladium-NHC complexes are a family of organopalladium compounds in which palladium forms a coordination complex with N-heterocyclic carbenes (NHCs). They have been investigated for applications in homogeneous catalysis, particularly cross-coupling reactions.
In organic chemistry, the Fujiwara–Moritani reaction is a type of cross coupling reaction where an aromatic C-H bond is directly coupled to an olefinic C-H bond, generating a new C-C bond. This reaction is performed in the presence of a transition metal, typically palladium. The reaction was discovered by Yuzo Fujiwara and Ichiro Moritani in 1967. An external oxidant is required to this reaction to be run catalytically. Thus, this reaction can be classified as a C-H activation reaction, an oxidative Heck reaction, and a C-H olefination. Surprisingly, the Fujiwara–Moritani reaction was discovered before the Heck reaction.
Dialkylbiaryl phosphine ligands are phosphine ligands that are used in homogeneous catalysis. They have proved useful in Buchwald-Hartwig amination and etherification reactions as well as Negishi cross-coupling, Suzuki-Miyaura cross-coupling, and related reactions. In addition to these Pd-based processes, their use has also been extended to transformations catalyzed by nickel, gold, silver, copper, rhodium, and ruthenium, among other transition metals.
Mark Stradiotto is a Canadian chemist. He is currently the Arthur B. McDonald Research Chair and the Alexander McLeod Professor of Chemistry in the Department of Chemistry at Dalhousie University.
Miyaura borylation, also known as the Miyaura borylation reaction, is a named reaction in organic chemistry that allows for the generation of boronates from vinyl or aryl halides with the cross-coupling of bis(pinacolato)diboron in basic conditions with a catalyst such as PdCl2(dppf). The resulting borylated products can be used as coupling partners for the Suzuki reaction.
Heterogeneous metal catalyzed cross-coupling is a subset of metal catalyzed cross-coupling in which a heterogeneous metal catalyst is employed. Generally heterogeneous cross-coupling catalysts consist of a metal dispersed on an inorganic surface or bound to a polymeric support with ligands. Heterogeneous catalysts provide potential benefits over homogeneous catalysts in chemical processes in which cross-coupling is commonly employed—particularly in the fine chemical industry—including recyclability and lower metal contamination of reaction products. However, for cross-coupling reactions, heterogeneous metal catalysts can suffer from pitfalls such as poor turnover and poor substrate scope, which have limited their utility in cross-coupling reactions to date relative to homogeneous catalysts. Heterogeneous metal catalyzed cross-couplings, as with homogeneous metal catalyzed ones, most commonly use Pd as the cross-coupling metal.
References
- ↑ "People | Department of Chemistry - UC Santa Barbara". www.chem.ucsb.edu.
- ↑ "Past Award Entries and Recipients | Green Chemistry | US EPA" . Retrieved 12 August 2023.
- ↑ "Zymes llc". Archived from the original on July 17, 2008.
- ↑ TPGS-750-M: A Second-Generation Amphiphile for Metal-Catalyzed Cross-Couplings in Water at Room Temperature
- ↑ “Nok”: A Phytosterol-Based Amphiphile Enabling Transition-Metal-Catalyzed Couplings in Water at Room Temperature
- ↑ Sustainable Fe–ppm Pd nanoparticle catalysis of Suzuki-Miyaura cross-couplings in water
- ↑ HandaPhos: A General Ligand Enabling Sustainable ppm Levels of Palladium-Catalyzed Cross-Couplings in Water at Room Temperature
- ↑ β-(Trimethylsilyl)ethoxymethyl chloride. A new reagent for the protection of the hydroxyl group
- ↑ Simplification of the Mitsunobu Reaction. Di-p-chlorobenzyl Azodicarboxylate: A New Azodicarboxylate
- ↑ (BDP)CuH: A "Hot" Stryker's reagent for Use in Achiral Conjugate Reductions
- ↑ Asymmetric Hydrosilylation of Aryl Ketones Catalyzed by Copper Hydride Complexed by Nonracemic Biphenyl Bis-phosphine Ligands
- ↑ Bruce H. Lipshutz, Robert Moretti, Robert Crow "Mixed Higher-order Cyanocuprate-induced Epoxide Openings: 1-Benzyloxy-4-penten-2-ol" Org. Synth. 1990, volume 69, pp. 80. {{DOI:10.15227/orgsyn.069.0080}}
- ↑ Handa, Sachin; Andersson, Martin P.; Gallou, Fabrice; Reilly, John; Lipshutz, Bruce H. (2016). "Handa Phos: A General Ligand Enabling Sustainable PPM Levels of Palladium-Catalyzed Cross-Couplings in Water at Room Temperature". Angewandte Chemie International Edition. 55 (16): 4914–4918. doi:10.1002/anie.201510570. PMC 4966530 . PMID 26924396.
- ↑ Landstrom, Evan B.; Handa, Sachin; Aue, Donald H.; Gallou, Fabrice; Lipshutz, Bruce H. (2018). "Evan Phos: A ligand for PPM level Pd-catalyzed Suzuki–Miyaura couplings in either organic solvent or water". Green Chemistry. 20 (15): 3436–3443. doi:10.1039/C8GC01356J.
- ↑ "Merck KGaA". Archived from the original on 2016-11-12. Retrieved 2019-06-16.
- ↑ "NSF - OLPA - News Tip: November 29, 2002". www.nsf.gov.
- ↑ Lipshutz, Bruce H.; Lower, Asher; Berl, Volker; Schein, Karin; Wetterich, Frank (2005). "An Improved Synthesis of the "Miracle Nutrient" Coenzyme Q10". Organic Letters. 7 (19): 4095–4097. doi:10.1021/ol051329y. PMID 16146360.
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