Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide, cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. Metal β-diketonates, alkoxides, dialkylamides, and metal phosphine complexes are representative members of this class. The field of organometallic chemistry combines aspects of traditional inorganic and organic chemistry.
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 or Suzuki coupling is an organic reaction that uses a palladium complex catalyst to cross-couple a boronic acid to an organohalide. 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 noble metal catalysis in organic synthesis. This reaction is sometimes telescoped with the related Miyaura borylation; the combination is the Suzuki–Miyaura reaction. It is widely used to synthesize polyolefins, styrenes, and substituted biphenyls.
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.
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.
Transmetalation (alt. spelling: transmetallation) is a type of organometallic reaction that involves the transfer of ligands from one metal to another. It has the general form:
Organoaluminium chemistry is the study of compounds containing bonds between carbon and aluminium. It is one of the major themes within organometallic chemistry. Illustrative organoaluminium compounds are the dimer trimethylaluminium, the monomer triisobutylaluminium, and the titanium-aluminium compound called Tebbe's reagent. The behavior of organoaluminium compounds can be understood in terms of the polarity of the C−Al bond and the high Lewis acidity of the three-coordinated species. Industrially, these compounds are mainly used for the production of polyolefins.
A carbometallation is any reaction where a carbon-metal bond reacts with a carbon-carbon π-bond to produce a new carbon-carbon σ-bond and a carbon-metal σ-bond. The resulting carbon-metal bond can undergo further carbometallation reactions or it can be reacted with a variety of electrophiles including halogenating reagents, carbonyls, oxygen, and inorganic salts to produce different organometallic reagents. Carbometallations can be performed on alkynes and alkenes to form products with high geometric purity or enantioselectivity, respectively. Some metals prefer to give the anti-addition product with high selectivity and some yield the syn-addition product. The outcome of syn and anti- addition products is determined by the mechanism of the carbometallation.
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.
The Glaser coupling is a type of coupling reaction. It is by far the oldest acetylenic coupling and is based on cuprous salts like copper(I) chloride or copper(I) bromide and an additional oxidant like oxygen. The base in its original scope is ammonia. The solvent is water or an alcohol. The reaction was first reported by Carl Andreas Glaser in 1869. He suggested the following process for his way to diphenylbutadiyne:
Makoto Kumada was a Japanese chemist and was a Professor of Chemistry first at Osaka City University until his retirement in 1983 at Kyoto University in Japan. In 1972, Kumada's group reported nickel-catalyzed cross coupling reactions nearly concurrently with the Corriu group working in France. The Kumada coupling now bears his name.
Ei-ichi Negishi was a Japanese chemist who was best known for his discovery of the Negishi coupling. He spent most of his career at Purdue University in the United States, where he was the Herbert C. Brown Distinguished Professor and the director of the Negishi-Brown Institute. He was awarded the 2010 Nobel Prize in Chemistry "for palladium catalyzed cross couplings in organic synthesis" jointly with Richard F. Heck and Akira Suzuki.
John Kenneth Stille was an American chemist who discovered the Stille reaction. He received B.A. and M.A. degrees from the University of Arizona before serving in the Navy during the Korean War. He received his Ph.D. from the University of Illinois, where he studied under Carl Shipp Marvel. Stille began his independent career at the University of Iowa in 1957 before moving to Colorado State University in 1977.
Richard Frederick Heck was an American chemist noted for the discovery and development of the Heck reaction, which uses palladium to catalyze organic chemical reactions that couple aryl halides with alkenes. The analgesic naproxen is an example of a compound that is prepared industrially using the Heck reaction.
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:
Akira Suzuki is a Japanese chemist and Nobel Prize Laureate (2010), who first published the Suzuki reaction, the organic reaction of an aryl- or vinyl-boronic acid with an aryl- or vinyl-halide catalyzed by a palladium(0) complex, in 1979.
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.
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.
Norio Miyaura was a Japanese organic chemist. He was a professor of graduate chemical engineering at Hokkaido University. His major accomplishments surrounded his work in cross-coupling reactions / conjugate addition reactions of organoboronic acids and addition / coupling reactions of diborons and boranes. He is also the co-author of Cross-Coupling Reactions: A Practical Guide with M. Nomura E. S.. Miyaura was a world-known and accomplished researcher by the time he retired and so, in 2007, he won the Japan Chemical Society Award.
The Murahashi Coupling is a cross coupling reaction. The coupling partners are organolithiums and organic halides. Transition metal catalysts are required. The reaction was first reported by Shun-Ichi Murahashi in 1974. This reaction is notable for using organolithiums as opposed to other cross-coupling reactions which utilize various metal-carbon compounds. Since the production of these other coupling reagents relies heavily upon organolithiums, in bypassing these intermediates, this process is much more efficient. It has further been shown that the Murahashi reaction proceeds with greater selectivity, faster reaction times, and lower reaction temperatures than other similar coupling reactions while maintaining similar or higher yields.
