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 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.
Organopalladium chemistry is a branch of organometallic chemistry that deals with organic palladium compounds and their reactions. Palladium is often used as a catalyst in the reduction of alkenes and alkynes with hydrogen. This process involves the formation of a palladium-carbon covalent bond. Palladium is also prominent in carbon-carbon coupling reactions, as demonstrated in tandem reactions.
Crabtree's catalyst is an organoiridium compound with the formula [C8H12IrP(C6H11)3C5H5N]PF6. It is a homogeneous catalyst for hydrogenation and hydrogen-transfer reactions, developed by Robert H. Crabtree. This air stable orange solid is commercially available and known for its directed hydrogenation to give trans stereoselectivity with respective of directing group.
Carbonylation refers to reactions that introduce carbon monoxide into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbonylation also refers to oxidation of protein side chains.
In organometallic chemistry, a migratory insertion is a type of reaction wherein two ligands on a metal complex combine. It is a subset of reactions that very closely resembles the insertion reactions, and both are differentiated by the mechanism that leads to the resulting stereochemistry of the products. However, often the two are used interchangeably because the mechanism is sometimes unknown. Therefore, migratory insertion reactions or insertion reactions, for short, are defined not by the mechanism but by the overall regiochemistry wherein one chemical entity interposes itself into an existing bond of typically a second chemical entity e.g.:
3,3′,3′′-Phosphanetriyltris(benzenesulfonic acid) trisodium salt (abbreviated TPPTS), is an organic compound that is also known as sodium triphenylphosphine trisulfonate. The compound has the formula P(C6H4SO3Na)3. This white solid is an unusual example of a water-soluble phosphine. Its complexes are also water-soluble. Its complex with rhodium is used in the industrial production of butyraldehyde.
Organoruthenium chemistry is the chemistry of organometallic compounds containing a carbon to ruthenium chemical bond. Several organoruthenium catalysts are of commercial interest and organoruthenium compounds have been considered for cancer therapy. The chemistry has some stoichiometric similarities with organoiron chemistry, as iron is directly above ruthenium in group 8 of the periodic table. The most important reagents for the introduction of ruthenium are ruthenium(III) chloride and triruthenium dodecacarbonyl.
Organogold chemistry is the study of compounds containing gold–carbon bonds. They are studied in academic research, but have not received widespread use otherwise. The dominant oxidation states for organogold compounds are I with coordination number 2 and a linear molecular geometry and III with CN = 4 and a square planar molecular geometry. The first organogold compound discovered was gold(I) carbide Au2C2, which was first prepared in 1900.
Organoplatinum chemistry is the chemistry of organometallic compounds containing a carbon to platinum chemical bond, and the study of platinum as a catalyst in organic reactions. Organoplatinum compounds exist in oxidation state 0 to IV, with oxidation state II most abundant. The general order in bond strength is Pt-C (sp) > Pt-O > Pt-N > Pt-C (sp3). Organoplatinum and organopalladium chemistry are similar, but organoplatinum compounds are more stable and therefore less useful as catalysts.
A metal-phosphine complex is a In 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).
Brookhart's acid is the salt of the diethyl ether oxonium ion and tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAr′4). It is a colorless solid, used as a strong acid. The compound was first reported by Volpe, Grant, and Brookhart in 1992.
Phosphinooxazolines are a class of chiral ligands used in asymmetric catalysis. Their complexes are particularly effective at generating single enatiomers in reactions involving highly symmetric transition states, such as allylic substitutions, which are typically difficult to perform stereoselectively. The ligands are bidentate and have been shown to be hemilabile with the softer P‑donor being more firmly bound than the harder N‑donor.
Hydrophosphination is the insertion of a carbon-carbon multiple bond into a phosphorus-hydrogen bond forming a new phosphorus-carbon bond. Like other hydrofunctionalizations, the rate and regiochemistry of the insertion reaction is influenced by the catalyst. Catalysts take many forms, but most prevalent are bases and free-radical initiators.
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, hydrovinylation is the formal insertion of an alkene into the C-H bond of ethylene. The more general reaction, hydroalkenylation, is the formal insertion of an alkene into the C-H bond of any terminal alkene. The reaction is catalyzed by metal complexes. A representative reaction is the conversion of styrene and ethylene to 3-phenybutene:
Heterobimetallic catalysis is an approach to catalysis that employs two different metals to promote a chemical reaction. Included in this definition are cases where: 1) each metal activates a different substrate, 2) both metals interact with the same substrate, and 3) only one metal directly interacts with the substrate(s), while the second metal interacts with the first.
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.
1,1,1-Tris(diphenylphosphinomethyl)ethane, also called Triphos, is an organophosphorus compound with the formula CH3C[CH2PPh2]3. An air-sensitive white solid, it is a tripodal ligand ("three-legged") of idealized C3v symmetry. It was originally prepared by the reaction of sodium diphenylphosphide and CH3C(CH2Cl)3:
