The Journal of the American Chemical Society (also known as JACS) is a weekly peer-reviewed scientific journal that was established in 1879 by the American Chemical Society. The journal has absorbed two other publications in its history, the Journal of Analytical and Applied Chemistry (July 1893) and the American Chemical Journal (January 1914). It publishes original research papers in all fields of chemistry. Since 2002, the journal is edited by Peter J. Stang (University of Utah). In 2014, the journal moved to a hybrid open access publishing model.
|Journal of the American Chemical Society|
|Edited by||Peter J. Stang|
American Chemical Society (United States)
|J. Am. Chem. Soc.|
The Journal of the American Chemical Society is abstracted and indexed in Chemical Abstracts Service, Scopus, EBSCOhost, Thomson-Gale, ProQuest, PubMed, Web of Science, and SwetsWise. According to the Journal Citation Reports, it has an impact factor of 14.357 for 2017.
The aldol reaction is a means of forming carbon–carbon bonds in organic chemistry.
Discovered independently by the Russian chemist Alexander Borodin in 1869 and by the French chemist Charles-Adolphe Wurtz in 1872, the reaction combines two carbonyl compounds (the original experiments used aldehydes) to form a new β-hydroxy carbonyl compound. These products are known as aldols, from the aldehyde + alcohol, a structural motif seen in many of the products. Aldol structural units are found in many important molecules, whether naturally occurring or synthetic.
For example, the aldol reaction has been used in the large-scale production of the commodity chemical pentaerythritol
and the synthesis of the heart disease drug Lipitor (atorvastatin, calcium salt).The aldol reaction unites two relatively simple molecules into a more complex one. Increased complexity arises because up to two new stereogenic centers (on the α- and β-carbon of the aldol adduct, marked with asterisks in the scheme below) are formed. Modern methodology is capable of not only allowing aldol reactions to proceed in high yield but also controlling both the relative and absolute configuration of these stereocenters. This ability to selectively synthesize a particular stereoisomer is significant because different stereoisomers can have very different chemical and biological properties.
For example, stereogenic aldol units are especially common in polyketides, a class of molecules found in biological organisms. In nature, polyketides are synthesized by enzymes that effect iterative Claisen condensations. The 1,3-dicarbonyl products of these reactions can then be variously derivatized to produce a wide variety of interesting structures. Often, such derivitization involves the reduction of one of the carbonyl groups, producing the aldol subunit. Some of these structures have potent biological properties: the immunosuppressant FK506, the anti-tumor agent discodermolide, or the antifungal agent amphotericin B, for example. Although the synthesis of many such compounds was once considered nearly impossible, aldol methodology has allowed their efficient synthesis in many cases.
A typical modern aldol addition reaction, shown above, might involve the nucleophilic addition of a ketone enolate to an aldehyde. Once formed, the aldol product can sometimes lose a molecule of water to form an α,β-unsaturated carbonyl compound. This is called aldol condensation. A variety of nucleophiles may be employed in the aldol reaction, including the enols, enolates, and enol ethers of ketones, aldehydes, and many other carbonyl compounds. The electrophilic partner is usually an aldehyde or ketone (many variations, such as the Mannich reaction, exist). When the nucleophile and electrophile are different, the reaction is called a crossed aldol reaction; on the converse, when the nucleophile and electrophile are the same, the reaction is called an aldol dimerization.Asymmetric hydrogenation
Asymmetric hydrogenation is a chemical reaction that adds two atoms of hydrogen preferentially to one of two faces of an unsaturated substrate molecule, such as an alkene or ketone. The selectivity derives from the manner that the substrate binds to the chiral catalysts. In jargon, this binding transmits spatial information (what chemists refer to as chirality) from the catalyst to the target, favoring the product as a single enantiomer. This enzyme-like selectivity is particularly applied to bioactive products such as pharmaceutical agents and agrochemicals.Bicycloaromaticity
Bicycloaromaticity in chemistry is an extension of the concept of homoaromaticity with two aromatic ring currents situated in a non-planar molecule and sharing the same electrons. The concept originates with Melvin Goldstein who first reported about it in 1967. It is of some importance in academic research. Using MO theory the bicyclo[3.2.2]nonatrienyl cation was predicted to be destabilised and the corresponding anion predicted to be stabilised by bicycloaromaticity.
Bicycloaromaticity has been studied by others in relation to the bicyclo[3.2.2]nonatrienyl cation and in relation to specific carbanions . In 2017 experimental evidence was reported for bicycloaromaticity (dual aromaticity) to exist in a bicyclic porphyrinoid. This system has been described as aromatic with two ring systems of 26 (n=6) and 34 (n=8) electrons. By oxidation, another system was described as a triplet-state biradical, again considered aromatic by application of Baird's rule.Copper hydride
Copper hydride (also systematically named poly[cuprane(1)]) is a pyrophoric, inorganic compound with the chemical formula (CuH)n (also written as [CuH]n or CuH). It is an odourless, metastable, red solid, rarely isolated as a pure composition, that decomposes to the elements. Copper hydride is mainly produced as a reducing agent in organic synthesis and as a precursor to extremely reactive catalysts.Corannulene
Corannulene is a polycyclic aromatic hydrocarbon with chemical formula C20H10. The molecule consists of a cyclopentane ring fused with 5 benzene rings, so another name for it is circulene. It is of scientific interest because it is a geodesic polyarene and can be considered a fragment of buckminsterfullerene. Due to this connection and also its bowl shape, corannulene is also known as a buckybowl. Corannulene exhibits a bowl-to-bowl inversion with an inversion barrier of 10.2 kcal/mol (42.7 kJ/mol) at −64 °C.Diels–Alder reaction
In organic chemistry, the Diels–Alder reaction is a chemical reaction between a conjugated diene and a substituted alkene, commonly termed the dienophile (also spelled dieneophile), to form a substituted cyclohexene derivative. It is the prototypical example of a pericyclic reaction with a concerted mechanism. More specifically, it is classified as a thermally-allowed [4+2] cycloaddition with Woodward–Hoffmann symbol [π4s + π2s]. It was first described by Otto Diels and Kurt Alder in 1928. For the discovery of this reaction, they were awarded the Nobel Prize in Chemistry in 1950. Through the simultaneous construction of two new carbon–carbon bonds, the Diels–Alder reaction provides a reliable way to form six-membered rings with good control over the regio- and stereochemical outcomes. Consequently, it has served as a powerful and widely applied tool for the introduction of chemical complexity in the synthesis of natural products and new materials. The underlying concept has also been applied to π-systems involving heteroatoms, such as carbonyls and imines, which furnish the corresponding heterocycles; this variant is known as the hetero-Diels–Alder reaction. The reaction has also been generalized to other ring sizes, although none of these generalizations have matched the formation of six-membered rings in terms of scope or versatility. Because of the negative values of ΔH° and ΔS° for a typical Diels–Alder reaction, the microscopic reverse of a Diels–Alder reactions becomes favorable at high temperatures, although this is of synthetic importance for only a limited range of Diels-Alder adducts, generally with some special structural features; this reverse reaction is known as the retro-Diels–Alder reaction.Frederick N. Tebbe
Frederick Nye Tebbe was a chemist known for his work on organometallic chemistry. Tebbe was born in Oakland, California on March 20, 1935. His father, Charles L. Tebbe, worked for the United States Forest Service so Fred’s early education took place in Montana, Oregon, Maryland and Pennsylvania. He married Margaret Manzer in 1960, and they had a son (Andy, born in 1966) and a daughter (Sarah, born in 1971). He died of pancreatic cancer at his home in Delaware on September 28, 1995.Lewis acid catalysis
In Lewis acid catalysis of organic reactions, a metal-based Lewis acid acts as an electron pair acceptor to increase the reactivity of a substrate. Common Lewis acid catalysts are based on main group metals such as aluminum, boron, silicon, and tin, as well as many early (titanium, zirconium) and late (iron, copper, zinc) d-block metals. The metal atom forms an adduct with a lone-pair bearing electronegative atom in the substrate, such as oxygen (both sp2 or sp3), nitrogen, sulfur, and halogens. The complexation has partial charge-transfer character and makes the lone-pair donor effectively more electronegative, activating the substrate toward nucleophilic attack, heterolytic bond cleavage, or cycloaddition with 1,3-dienes and 1,3-dipoles.Many classical reactions involving carbon–carbon or carbon–heteroatom bond formation can be catalyzed by Lewis acids. Examples include the Friedel-Crafts reaction, the aldol reaction, and various pericyclic processes that proceed slowly at room temperature, such as the Diels-Alder reaction and the ene reaction. In addition to accelerating the reactions, Lewis acid catalysts are able to impose regioselectivity and stereoselectivity in many cases.
Early developments in Lewis acid reagents focused on easily available compounds such as TiCl4, BF3, SnCl4, and AlCl3. The relative strengths of these (and other) Lewis acids may be estimated from NMR spectroscopy by the Childs method or the Gutmann-Beckett method. Over the years, versatile catalysts bearing ligands designed for specific applications have facilitated improvement in both reactivity and selectivity of Lewis acid-catalyzed reactions. More recently, Lewis acid catalysts with chiral ligands have become an important class of tools for asymmetric catalysis.Challenges in the development of Lewis acid catalysis include inefficient catalyst turnover (caused by catalyst affinity for the product) and the frequent requirement of two-point binding for stereoselectivity, which often necessitates the use of auxiliary groups.Molecular machine
A molecular machine, nanite, or nanomachine, refers to any discrete number of molecular components that produce quasi-mechanical movements (output) in response to specific stimuli (input). In biology, macromolecular machines frequently perform tasks essential for life such as DNA replication and ATP synthesis. The expression is often more generally applied to molecules that simply mimic functions that occur at the macroscopic level. The term is also common in nanotechnology where a number of highly complex molecular machines have been proposed that are aimed at the goal of constructing a molecular assembler.
For the last several decades, chemists and physicists alike have attempted, with varying degrees of success, to miniaturize machines found in the macroscopic world. Molecular machines research is currently at the forefront with the 2016 Nobel Prize in Chemistry being awarded to Jean-Pierre Sauvage, Sir J. Fraser Stoddart and Bernard L. Feringa for the design and synthesis of molecular machines.Moses Gomberg
Moses Gomberg (February 8, 1866 – February 12, 1947) was a chemistry professor at the University of Michigan.Organic synthesis
Organic synthesis is a special branch of chemical synthesis and is concerned with the intentional construction of organic compounds. Organic molecules are often more complex than inorganic compounds, and their synthesis has developed into one of the most important branches of organic chemistry. There are several main areas of research within the general area of organic synthesis: total synthesis, semisynthesis, and methodology.Organogold chemistry
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.Organotantalum chemistry
Organotantalum chemistry is the chemistry of chemical compounds containing a carbon-to-tantalum chemical bond. A wide variety of compound have been reported, initially with cyclopentadienyl and CO ligands. Oxidation states vary from Ta(V) to Ta(-I).Oxocarbon
An oxocarbon or oxide of carbon is a chemical compound consisting only of carbon and oxygen.The simplest and most common oxocarbons are carbon monoxide (CO) and carbon dioxide (CO2) with IUPAC names carbon(II) oxide and carbon(IV) oxide respectively. Many other stable (practically if not thermodynamically) or metastable oxides of carbon are known, but they are rarely encountered, such as carbon suboxide (C3O2 or O=C=C=C=O) and mellitic anhydride (C12O9).
While textbooks will often list only the first three, and rarely the fourth, a large number of other oxides are known today, most of them synthesized since the 1960s. Some of these new oxides are stable at room temperature. Some are metastable or stable only at very low temperatures, but decompose to simpler oxocarbons when warmed. Many are inherently unstable and can be observed only momentarily as intermediates in chemical reactions or are so reactive that they can exist only in the gas phase or under matrix isolation conditions.
The inventory of oxocarbons appears to be steadily growing. The existence of graphene oxide and of other stable polymeric carbon oxides with unbounded molecular structures suggests that many more remain to be discovered.Peter J. Stang
Peter John Stang (born November 17, 1941) is a German American chemist and Distinguished Professor of chemistry at the University of Utah. He has been the editor of the Journal of the American Chemical Society since 2002.Saul Winstein
Saul Winstein (October 8, 1912 – November 23, 1969) was a Canadian chemist who discovered the Winstein reaction. He argued a non-classical cation was needed to explain the stability of the norbornyl cation. This fueled a debate with Herbert C. Brown over the existence of σ-delocalized carbocations. Winstein also first proposed the concept of an intimate ion pair. He was co-author of the Grunwald-Winstein equation, concerning solvolysis rates.Richard F. Heck, who earlier in his career had undertaken postgraduate studies with Winstein, won the 2010 Nobel Prize in Chemistry.Superacid
According to the classical definition, a superacid is an acid with an acidity greater than that of 100% pure sulfuric acid, which has a Hammett acidity function (H0) of −12. According to the modern definition, a superacid is a medium in which the chemical potential of the proton is higher than in pure sulfuric acid. Commercially available superacids include trifluoromethanesulfonic acid (CF3SO3H), also known as triflic acid, and fluorosulfuric acid (HSO3F), both of which are about a thousand times stronger (i.e. have more negative H0 values) than sulfuric acid. Most strong superacids are prepared by the combination of a strong Lewis acid and a strong Brønsted acid. A strong superacid of this kind is fluoroantimonic acid. Another group of superacids, the carborane acid group, contains some of the strongest known acids.William Dale Phillips
William Dale Phillips was a chemist, nuclear magnetic resonance spectroscopist, federal science policy advisor and member of the National Academy of Sciences. He was born October 10, 1925, in Kansas City, Missouri and died in St. Louis, Missouri, on December 15, 1993.Wolff–Kishner reduction
The Wolff–Kishner reduction is a reaction used in organic chemistry to convert carbonyl functionalities into methylene groups. In the context of complex molecule synthesis, it is most frequently employed to remove a carbonyl group after it has served its synthetic purpose of activating an intermediate in a preceding step. As such, there is no obvious retron for this reaction. Originally reported by Nikolai Kischner in 1911 and Ludwig Wolff in 1912, it has been applied to the total synthesis of scopadulcic acid B, aspidospermidine and dysidiolide.
In general, the reaction mechanism first involves the in situ generation of a hydrazone by condensation of hydrazine with the ketone or aldehyde substrate. Sometimes it is however advantageous to use a pre-formed hydrazone as substrate (see modifications). The hydrazone is deprotonated by alkoxide base followed by a concerted, rate-determining step in which a diimide anion is formed. Collapse of this alkyldiimide with loss of N2 leads to formation of an alkylanion which can be protonated by solvent to give the desired product.
Because the Wolff–Kishner reduction requires highly basic conditions, it is unsuitable for base-sensitive substrates. However, this method can be superior over the related Clemmensen reduction for acid-sensitive compounds such as pyrroles and for high-molecular weight compounds.