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Carbenoid
In chemistry a carbenoid is a reactive intermediate that shares reaction characteristics with a carbene. In the Simmons–Smith reaction the carbenoid intermediate is a zinc / iodine complex that takes the form of :I-CH2-Zn-I This complex reacts with an alkene to form a cyclopropane just as a carbene would do. Carbenoids appear as intermediates in many other reactions. In one system a carbenoid chloroalkyllithium reagent is prepared in situ from a sulfoxide and t-BuLi which reacts the boronic ester to give an ate complex. The ate complex undergoes a 1,2-metallate rearrangement to give the homologated product, which is then further oxidised to a secondary alcohol.Iterative Stereospecific Reagent-Controlled Homologation of Pinacol Boronates by Enantioenriched -Chloroalkyllithium Reagents Paul R. Blakemore and Matthew S. Burge J. Am. Chem. Soc.; 2007; 129(11) pp 3068 - 3069; (Communication) : The enantiopurity of the chiral sulfoxide is preserved in the ultimate product after ox ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Simmons–Smith Reaction
The Simmons–Smith reaction is an organic cheletropic reaction involving an organozinc carbenoid that reacts with an alkene (or alkyne) to form a cyclopropane. It is named after Howard Ensign Simmons, Jr. and Ronald D. Smith. It uses a methylene free radical intermediate that is delivered to both carbons of the alkene simultaneously, therefore the configuration of the double bond is preserved in the product and the reaction is stereospecific. Mechanism Examples Thus, cyclohexene, diiodomethane, and a zinc-copper couple (as iodomethylzinc iodide, ) yield norcarane (bicyclo .1.0eptane). : The Simmons–Smith reaction is generally preferred over other methods of cyclopropanation, however it can be expensive due to the high cost of diiodomethane. Modifications involving cheaper alternatives have been developed, such as dibromomethane or diazomethane and zinc iodide. The reactivity of the system can also be increased by using the Furukawa modification, exchanging ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Carbene
In organic chemistry, a carbene is a molecule containing a neutral carbon atom with a Valence (chemistry), valence of two and two unshared valence electrons. The general formula is or where the R represents substituents or hydrogen atoms. The term "carbene" may also refer to the specific compound , also called methylene radical, methylene, the parent hydride from which all other carbene compounds are formally derived. There are two types of carbenes: singlet state, singlets or triplet state, triplets, depending upon their electronic structure. The different classes undergo different reactions. Most carbenes are extremely reactive and short-lived. A small number (the diHalogen, halocarbenes, carbon monoxide, and carbon monosulfide) can be isolated, and can stabilize as Coordination complex, metal ligands, but otherwise cannot be stored in bulk. A rare exception are the persistent carbenes, which have extensive application in modern organometallic chemistry. Generatio ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Alkene
In organic chemistry, an alkene, or olefin, is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or at the terminal position. Terminal alkenes are also known as Alpha-olefin, α-olefins. The International Union of Pure and Applied Chemistry (IUPAC) Preferred IUPAC name, recommends using the name "alkene" only for Open-chain compound, acyclic hydrocarbons with just one double bond; alkadiene, alkatriene, etc., or polyene for acyclic hydrocarbons with two or more double bonds; cycloalkene, cycloalkadiene, etc. for Cyclic compound, cyclic ones; and "olefin" for the general class – cyclic or acyclic, with one or more double bonds. Acyclic alkenes, with only one double bond and no other functional groups (also known as mono-enes) form a homologous series of hydrocarbons with the general formula with ''n'' being a >1 natural number (which is two hydrogens less than the corresponding alkane). When ''n'' is four or more, isomers are possible, ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Silylenoid
A silylenoid in organosilicon chemistry is a type of chemical compound with the general structure where R is any organic residue, X a halogen and M a metal. Silylenoids are the silicon pendants of carbenoid and both compounds have carbene or silylene like properties. Silylenoids are encountered as reactive intermediates in chemical reactions. A stable silylenoid can be prepared by reaction of a fluorobromosilane with a silyllithium compound in THF : :(t-Bu2MeSi)2SiFBr + t-Bu2MeSiLi/THF → (t-Bu2MeSi)2SiFLi.3THF + t-Bu2MeSiBr In this silylenoid the silicon atom is bonded with three substituents and not the usual four. X-ray diffraction shows that the Si-F bond with 170 pm is longer than usual for fluorosilanes. The F-Li bond is ionic with an estimated (in silico) positive charge of 0.88 residing on lithium and a negative charge of 0.74 on fluorine making it a (t-Bu2MeSi)2SiF−, Li+.3THF salt. The Si-F bond is likewise polarized with only 10% of the charge on silicon. When the ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chemistry
Chemistry is the scientific study of the properties and behavior of matter. It is a physical science within the natural sciences that studies the chemical elements that make up matter and chemical compound, compounds made of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they undergo during chemical reaction, reactions with other chemical substance, substances. Chemistry also addresses the nature of chemical bonds in chemical compounds. In the scope of its subject, chemistry occupies an intermediate position between physics and biology. It is sometimes called the central science because it provides a foundation for understanding both Basic research, basic and Applied science, applied scientific disciplines at a fundamental level. For example, chemistry explains aspects of plant growth (botany), the formation of igneous rocks (geology), how atmospheric ozone is formed and how environmental pollutants are degraded (ecology), the prop ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Reactive Intermediate
In chemistry, a reactive intermediate or an intermediate is a short-lived, high-energy, highly reactive molecule. When generated in a chemical reaction, it will quickly convert into a more stable molecule. Only in exceptional cases can these compounds be isolated and stored, e.g. low temperatures, matrix isolation. When their existence is indicated, reactive intermediates can help explain how a chemical reaction takes place. Most chemical reactions take more than one elementary step to complete, and a reactive intermediate is a high-energy, hence unstable, product that exists only in one of the intermediate steps. The series of steps together make a reaction mechanism. A reactive intermediate differs from a reactant or product or a simple reaction intermediate only in that it cannot usually be isolated but is sometimes observable only through fast spectroscopic methods. It is stable in the sense that an elementary reaction forms the reactive intermediate and the elementary rea ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Zinc
Zinc is a chemical element; it has symbol Zn and atomic number 30. It is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic table. In some respects, zinc is chemically similar to magnesium: both elements exhibit only one normal oxidation state (+2), and the Zn2+ and Mg2+ ions are of similar size. Zinc is the 24th most abundant element in Earth's crust and has five stable isotopes. The most common zinc ore is sphalerite (zinc blende), a zinc sulfide mineral. The largest workable lodes are in Australia, Asia, and the United States. Zinc is refined by froth flotation of the ore, roasting, and final extraction using electricity ( electrowinning). Zinc is an essential trace element for humans, animals, plants and for microorganisms and is necessary for prenatal and postnatal development. It is the second most abundant trace metal in humans after iron, an import ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Iodine
Iodine is a chemical element; it has symbol I and atomic number 53. The heaviest of the stable halogens, it exists at standard conditions as a semi-lustrous, non-metallic solid that melts to form a deep violet liquid at , and boils to a violet gas at . The element was discovered by the French chemist Bernard Courtois in 1811 and was named two years later by Joseph Louis Gay-Lussac, after the Ancient Greek , meaning 'violet'. Iodine occurs in many oxidation states, including iodide (I−), iodate (), and the various periodate anions. As the heaviest essential mineral nutrient, iodine is required for the synthesis of thyroid hormones. Iodine deficiency affects about two billion people and is the leading preventable cause of intellectual disabilities. The dominant producers of iodine today are Chile and Japan. Due to its high atomic number and ease of attachment to organic compounds, it has also found favour as a non-toxic radiocontrast material. Because of the spec ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Complex (chemistry)
A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many metal-containing compounds, especially those that include transition metals (elements like titanium that belong to the periodic table's d-block), are coordination complexes. Nomenclature and terminology Coordination complexes are so pervasive that their structures and reactions are described in many ways, sometimes confusingly. The atom within a ligand that is bonded to the central metal atom or ion is called the donor atom. In a typical complex, a metal ion is bonded to several donor atoms, which can be the same or different. A polydentate (multiple bonded) ligand is a molecule or ion that bonds to the central atom through several of the ligand's atoms; ligands with 2, 3, 4 or even 6 bonds to the central a ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Cyclopropane
Cyclopropane is the cycloalkane with the molecular formula (CH2)3, consisting of three methylene groups (CH2) linked to each other to form a triangular ring. The small size of the ring creates substantial ring strain in the structure. Cyclopropane itself is mainly of theoretical interest but many of its derivatives - cyclopropanes - are of commercial or biological significance. Cyclopropane was used as a clinical inhalational anesthetic from the 1930s through the 1980s. The substance's high flammability poses a risk of fire and explosions in operating rooms due to its tendency to accumulate in confined spaces, as its density is higher than that of air. History Cyclopropane was discovered in 1881 by August Freund, who also proposed the correct structure for the substance in his first paper. Freund treated 1,3-Dibromopropane, 1,3-dibromopropane with sodium, causing an intramolecular Wurtz reaction leading directly to cyclopropane. The yield of the reaction was improved by Gustavson ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Sulfoxide
In organic chemistry, a sulfoxide, also called a sulphoxide, is an organosulfur compound containing a sulfinyl () functional group attached to two carbon atoms. It is a polar functional group. Sulfoxides are oxidized derivatives of sulfides. Examples of important sulfoxides are alliin, a precursor to the compound that gives freshly crushed garlic its aroma, and dimethyl sulfoxide (DMSO), a common solvent. Structure and bonding Sulfoxides feature relatively short S–O distances. In DMSO, the S–O distance is 1.531 Å. The sulfur center is pyramidal; the sum of the angles at sulfur is about 306°.. Sulfoxides are generally represented with the structural formula R−S(=O)−R', where R and R' are organic groups. The bond between the sulfur and oxygen atoms is intermediate of a dative bond and a polarized double bond. The double-bond resonance form implies 10 electrons around sulfur (10-S-3 in N-X-L notation). The double-bond character of the S−O bond may be accou ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Tert-Butyllithium
''tert''-Butyllithium is a chemical compound with the Chemical formula, formula (CH3)3CLi. As an organolithium compound, it has applications in organic synthesis since it is a strong base (chemistry), base, capable of deprotonation, deprotonating many carbon molecules, including benzene. ''tert''-Butyllithium is available commercially as solutions in hydrocarbons (such as pentane); it is not usually prepared in the laboratory. Preparation ''tert''-Butyllithium is produced commercially by treating tert-butyl chloride with lithium. Its synthesis was first reported by R. B. Woodward in 1941. Structure and bonding Like other organolithium compounds, ''tert''-butyllithium is a cluster compound. Whereas n-Butyllithium, ''n''-butyllithium exists both as a hexamer and a tetramer, ''tert''-butyllithium exists exclusively as a tetramer with a cubane-type cluster, cubane structure. Bonding in organolithium clusters involves three-center two-electron bond, sigma delocalization and significan ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
