Jacobsen's Catalyst
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Jacobsen's Catalyst
Jacobsen's catalyst is the common name for N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane­diaminomanganese(III) chloride, a coordination compound of manganese and a salen ligand, salen-type ligand. It is used as an asymmetric catalyst in the Jacobsen epoxidation, which is renowned for its ability to enantioselectively transform prochiral alkenes into epoxides. Before its development, catalysts for the asymmetric epoxidation of alkenes required the substrate to have a directing functional group, such as an alcohol as seen in the Sharpless epoxidation. This compound has two enantiomers, which give the appropriate epoxide product from the alkene starting material. Enantiomerically pure epoxides are desirable as building blocks for complex molecules with specific chirality. Biologically active compounds can exhibit radically different activity based on differences in chirality and therefore the ability to obtain desired stereocenters in a molecule is of great importance to ...
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Coordination Compound
A coordination complex consists 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 atom are common. These compl ...
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Conjugated System
In theoretical chemistry, a conjugated system is a system of connected p-orbitals with delocalized electrons in a molecule, which in general lowers the overall energy of the molecule and increases stability. It is conventionally represented as having alternating single and multiple bonds. Lone pairs, radicals or carbenium ions may be part of the system, which may be cyclic, acyclic, linear or mixed. The term "conjugated" was coined in 1899 by the German chemist Johannes Thiele. Conjugation is the overlap of one p-orbital with another across an adjacent σ bond (in transition metals, d-orbitals can be involved). A conjugated system has a region of overlapping p-orbitals, bridging the interjacent locations that simple diagrams illustrate as not having a π bond. They allow a delocalization of π electrons across all the adjacent aligned p-orbitals. The π electrons do not belong to a single bond or atom, but rather to a group of atoms. Molecules containing conjugated syst ...
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Salen Ligand
Salen refers to a tetradentate C2-symmetric ligand synthesized from salicylaldehyde (sal) and ethylenediamine (en). It may also refer to a class of compounds, which are structurally related to the classical salen ligand, primarily bis-Schiff bases. Salen ligands are notable for coordinating a wide range of different metals, which they can often stabilise in various oxidation states. For this reason salen-type compounds are used as metal deactivators. Metal salen complexes also find use as catalysts. Synthesis and properties H2salen may be synthesized by the condensation of ethylenediamine and salicylaldehyde. : Complexes of salen with metal cations may be made without isolating it from the reaction mixture. This is possible because the stability constant for the formation of the metal complexes are very high, due to the chelate effect. :H2L + Mn+ → ML(n−2)+ + 2 H+ where L stands for the ligand. The pyridine adduct of the cobalt(II) complex Co(salen)(py) ( salcomine) ...
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Enantiomers
In chemistry, an enantiomer ( /ɪˈnænti.əmər, ɛ-, -oʊ-/ ''ih-NAN-tee-ə-mər''; from Ancient Greek ἐνάντιος ''(enántios)'' 'opposite', and μέρος ''(méros)'' 'part') – also called optical isomer, antipode, or optical antipode – is one of two stereoisomers that are non-superposable onto their own mirror image. Enantiomers are much like one's right and left hands, when looking at the same face, they cannot be superposed onto each other. No amount of reorientation will allow the four unique groups on the chiral carbon (see Chirality (chemistry)) to line up exactly. The number of stereoisomers a molecule has can be determined by the number of chiral carbons it has. Stereoisomers include both enantiomers and diastereomers. Diastereomers, like enantiomers, share the same molecular formula and are non-superposable onto each other however, they are not mirror images of each other. A molecule with chirality rotates plane-polarized light. A mixture of equals amou ...
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Asymmetric Catalysis
Enantioselective synthesis, also called asymmetric synthesis, is a form of chemical synthesis. It is defined by IUPAC as "a chemical reaction (or reaction sequence) in which one or more new elements of chirality are formed in a substrate molecule and which produces the stereoisomeric (enantiomeric or diastereomeric) products in unequal amounts." Put more simply: it is the synthesis of a compound by a method that favors the formation of a specific enantiomer or diastereomer. Enantiomers are stereoisomers that have opposite configurations at every chiral center. Diastereomers are stereoisomers that differ at one or more chiral centers. Enantioselective synthesis is a key process in modern chemistry and is particularly important in the field of pharmaceuticals, as the different enantiomers or diastereomers of a molecule often have different biological activity. Overview Many of the building blocks of biological systems such as sugars and amino acids are produced exclusively as ...
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Lactones
Lactones are cyclic carboxylic esters, containing a 1-oxacycloalkan-2-one structure (), or analogues having unsaturation or heteroatoms replacing one or more carbon atoms of the ring. Lactones are formed by intramolecular esterification of the corresponding hydroxycarboxylic acids, which takes place spontaneously when the ring that is formed is five- or six-membered. Lactones with three- or four-membered rings (α-lactones and β-lactones) are very reactive, making their isolation difficult. Special methods are normally required for the laboratory synthesis of small-ring lactones as well as those that contain rings larger than six-membered. Nomenclature Lactones are usually named according to the precursor acid molecule (''aceto'' = 2 carbon atoms, ''propio'' = 3, ''butyro'' = 4, ''valero'' = 5, ''capro'' = 6, etc.), with a ''-lactone'' suffix and a Greek letter prefix that specifies the number of carbon atoms in the heterocycle — that is, the distance between the relevant -OH ...
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Carbonylation
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. Organic chemistry Several industrially useful organic chemicals are prepared by carbonylations, which can be highly selective reactions. Carbonylations produce organic carbonyls, i.e., compounds that contain the C=O functional group such as aldehydes, carboxylic acids and esters. Carbonylations are the basis of many types of reactions, including hydroformylation and Reppe reactions. These reactions require metal catalysts, which bind and activate the CO. These processes involve transition metal acyl complexes as intermediates. Much of this theme was developed by Walter Reppe. Hydroformylation Hydroformylation entails the addition of both carbon monoxide and hydrogen to unsaturated ...
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Styrene
Styrene () is an organic compound with the chemical formula C6H5CH=CH2. This derivative of benzene is a colorless oily liquid, although aged samples can appear yellowish. The compound evaporates easily and has a sweet smell, although high concentrations have a less pleasant odor. Styrene is the precursor to polystyrene and several copolymers. Approximately 25 million tonnes of styrene were produced in 2010, increasing to around 35 million tonnes by 2018. Natural occurrence Styrene is named after storax balsam (often commercially sold as ''styrax''), the resin of Liquidambar trees of the Altingiaceae plant family. Styrene occurs naturally in small quantities in some plants and foods (cinnamon, coffee beans, balsam tree (other), balsam trees and peanuts) and is also found in coal tar. History In 1839, the German apothecary Eduard Simon isolated a volatile liquid from the resin (called ''storax'' or ''styrax'' (Latin)) of the Liquidambar styraciflua, American sweetgu ...
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Approach Of Substrate 1
Approach may refer to: Aviation *Visual approach *Instrument approach *Final approach Music * ''Approach'' (album), by Von Hertzen Brothers * ''The Approach'', an album by I:Scintilla Other uses *Approach Beach, a gazetted beach in Ting Kau, Hong Kong *Approach shot (other) *Lotus Approach, a database *Bridge approach * Approaches to scientific method *Bowling action in the sport of cricket *Flirting See also *Capability approach, in economic theory *Final approach (other) In aeronautics, the final approach (also called the final leg and final approach leg) is the last leg in an aircraft's approach to landing, when the aircraft is lined up with the runway and descending for landing.Crane, Dale: ''Dictionary of ...
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Oxo (ligand)
A transition metal oxo complex is a coordination complex containing an oxo ligand. Formally O2-, an oxo ligand can be bound to one or more metal centers, i.e. it can exist as a terminal or (most commonly) as bridging ligands (Fig. 1). Oxo ligands stabilize high oxidation states of a metal.Nugent, W. A., Mayer, J. M. "Metal-Ligand Multiple Bonds." John Wiley & Sons, New York, 1988. They are also found in several metalloproteins, for example in molybdenum cofactors and in many iron-containing enzymes. One of the earliest synthetic compounds to incorporate an oxo ligand is potassium ferrate (K2FeO4), which was likely prepared by Georg E. Stahl in 1702. Reactivity Olation and acid-base reactions A common reaction exhibited by metal-oxo compounds is olation, the condensation process that converts low molecular weight oxides to polymers with M-O-M linkages. Olation often begins with the deprotonation of a metal-hydroxo complex. It is the basis for mineralization and the precipi ...
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Oxidation Des Katalysators V4
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a decrease in the oxidation state. There are two classes of redox reactions: * ''Electron-transfer'' – Only one (usually) electron flows from the reducing agent to the oxidant. This type of redox reaction is often discussed in terms of redox couples and electrode potentials. * ''Atom transfer'' – An atom transfers from one substrate to another. For example, in the rusting of iron, the oxidation state of iron atoms increases as the iron converts to an oxide, and simultaneously the oxidation state of oxygen decreases as it accepts electrons released by the iron. Although oxidation reactions are commonly associated with the formation of oxides, other chemical species can serve the same function. In hydrogenation, C=C (and other) bonds ar ...
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