|
Julia Olefination
The Julia olefination (also known as the Julia–Lythgoe olefination) is the chemical reaction used in organic chemistry of phenyl sulfones (1) with aldehydes (or ketones) to give alkenes (olefins)(3) after alcohol functionalization and reductive elimination using sodium amalgam or SmI2. The reaction is named after the French chemist Marc Julia. The utility of this connective olefination reaction arises from its versatility, its wide functional group tolerance, and the mild reaction conditions under which the reaction proceeds. All four steps can be carried out in a single reaction vessel, and use of R3X is optional. However, purification of the sulfone intermediate 2 leads to higher yield and purity. Most often R3 is acetyl or benzoyl, with acetic anhydride or benzoyl chloride used in the preparation of 2. History In 1973, Marc Julia and Jean-Marc Paris reported a novel olefin synthesis in which β-acyloxysulfones were reductively eliminated to the corresponding di-, tri-, o ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Marc Julia
Marc Julia (23 October 1922 – 29 June 2010) was a French chemist and the winner of the 1990 CNRS Gold Medal in chemistry. He discovered the Julia olefination reaction in 1973. Biography Julia was born in 1922 in Paris as son of the renowned mathematician Gaston Julia. Julia studied physics at the École Normale Supérieure. After receiving his diploma he joined the group of Ian Heilbron and David G. Jones at the Imperial College London Imperial College London (legally Imperial College of Science, Technology and Medicine) is a public research university in London, United Kingdom. Its history began with Prince Albert, consort of Queen Victoria, who developed his vision for a cu ... where he received his first PhD in 1948. Back to France he changed his subject to chemistry and subsequently received his second PhD for work with . References Further reading * * {{DEFAULTSORT:Julia, Marc 1922 births 2010 deaths 20th-century French chemists Members of the French Academy ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Alkoxide
In chemistry, an alkoxide is the conjugate base of an alcohol and therefore consists of an organic group bonded to a negatively charged oxygen atom. They are written as , where R is the organic substituent. Alkoxides are strong bases and, when R is not bulky, good nucleophiles and good ligands. Alkoxides, although generally not stable in protic solvents such as water, occur widely as intermediates in various reactions, including the Williamson ether synthesis. Transition metal alkoxides are widely used for coatings and as catalysts. Enolates are unsaturated alkoxides derived by deprotonation of a bond adjacent to a ketone or aldehyde. The nucleophilic center for simple alkoxides is located on the oxygen, whereas the nucleophilic site on enolates is delocalized onto both carbon and oxygen sites. Ynolates are also unsaturated alkoxides derived from acetylenic alcohols. Phenoxides are close relatives of the alkoxides, in which the alkyl group is replaced by a derivative of be ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Sodium Bis(trimethylsilyl)amide
Sodium bis(trimethylsilyl)amide is the organosilicon compound with the formula . This species, usually called NaHMDS (sodium hexamethyldisilazide), is a strong base used for deprotonation reactions or base-catalyzed reactions. Its advantages are that it is commercially available as a solid and it is soluble not only in ethers, such as THF or diethyl ether, but also in aromatic solvents, like benzene and toluene by virtue of the lipophilic TMS groups. NaHMDS is quickly destroyed by water to form sodium hydroxide and bis(trimethylsilyl)amine. Structure Although the Na–N bond is polar covalent as a solid, when dissolved in nonpolar solvents this compound is trimeric, consisting of a central ring. Applications in synthesis NaHMDS is used as a strong base in organic synthesis. Typical reactions: *To deprotonate ketones and esters to generate enolate derivatives. *Generate carbenes by dehydrohalogenation of halocarbons. These carbene reagents add to alkenes to give substituted cy ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Tetrazole
Tetrazoles are a class of synthetic organic heterocyclic compound, consisting of a 5-member ring of four nitrogen atoms and one carbon atom. The name tetrazole also refers to the parent compound with formula CH2N4, of which three isomers can be formulated. Structure and bonding Three isomers of the parent tetrazole exist, differing in the position of the double bonds: 1''H''-, 2''H''-, and 5''H''-tetrazole. The 1''H''- and 2''H''- isomers are tautomers, with the equilibrium lying on the side of 1''H''-tetrazole in the solid phase. In the gas phase, 2''H''-tetrazole dominates. These isomers can be regarded as aromatic, with 6 π-electrons, while the 5''H''-isomer is nonaromatic. Synthesis 1''H''-Tetrazole was first prepared by the reaction of anhydrous hydrazoic acid and hydrogen cyanide under pressure. Treatment of organic nitriles with sodium azide in the presence of iodine or silica-supported sodium bisulfate as a heterogeneous catalyst enables an advantageous synthesis ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Alkylation
Alkylation is the transfer of an alkyl group from one molecule to another. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion, or a carbene (or their equivalents). Alkylating agents are reagents for effecting alkylation. Alkyl groups can also be removed in a process known as dealkylation. Alkylating agents are often classified according to their nucleophilic or electrophilic character. In oil refining contexts, alkylation refers to a particular alkylation of isobutane with olefins. For upgrading of petroleum, alkylation produces a premium blending stock for gasoline. In medicine, alkylation of DNA is used in chemotherapy to damage the DNA of cancer cells. Alkylation is accomplished with the class of drugs called alkylating antineoplastic agents. Nucleophilic alkylating agents Nucleophilic alkylating agents deliver the equivalent of an alkyl anion ( carbanion). The formal "alkyl anion" attacks an electrophile, forming a new covalent ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
General Julia Kocienski Scheme
A general officer is an officer of high rank in the armies, and in some nations' air forces, space forces, and marines or naval infantry. In some usages the term "general officer" refers to a rank above colonel."general, adj. and n.". OED Online. March 2021. Oxford University Press. https://www.oed.com/view/Entry/77489?rskey=dCKrg4&result=1 (accessed May 11, 2021) The term ''general'' is used in two ways: as the generic title for all grades of general officer and as a specific rank. It originates in the 16th century, as a shortening of ''captain general'', which rank was taken from Middle French ''capitaine général''. The adjective ''general'' had been affixed to officer designations since the late medieval period to indicate relative superiority or an extended jurisdiction. Today, the title of ''general'' is known in some countries as a four-star rank. However, different countries use different systems of stars or other insignia for senior ranks. It has a NATO rank scal ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Philip Joseph Kocienski
Philip Joseph Kocienski (born 23 December 1946) is a British organic chemist. He is an Emeritus Professor at the University of Leeds. Research Kocienski has made contributions to the design and development of new organometallic reagents in synthesis, and the applications of synthetic methods to complex natural products. Early work with Basil Lythgoe on the scope and stereochemistry of the Julia olefination with alpha-metallated sulphone reagents emphasised the value of this method in organic chemistry. His major contribution has been to research the synthesis and chemistry of novel metallated (lithium, copper and nickel) enol ethers, and to develop the uses of these intermediates in the synthesis of oxacyclic and geometrically defined alkene units in natural products of biological significance. Kocienski has synthesised the insecticide milbemycin beta 3, the potassium channel blocker talaromycin B, the hypotensive agent lacrimin, and the antihypertensive agent zoapatanol. His ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Lithium
Lithium (from el, λίθος, lithos, lit=stone) is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid element. Like all alkali metals, lithium is highly reactive and flammable, and must be stored in vacuum, inert atmosphere, or inert liquid such as purified kerosene or mineral oil. When cut, it exhibits a metallic luster, but moist air corrodes it quickly to a dull silvery gray, then black tarnish. It never occurs freely in nature, but only in (usually ionic) compounds, such as pegmatitic minerals, which were once the main source of lithium. Due to its solubility as an ion, it is present in ocean water and is commonly obtained from brines. Lithium metal is isolated electrolytically from a mixture of lithium chloride and potassium chloride. The nucleus of the lithium atom verges on instability, since the two stable lithium isotopes foun ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Sulfur Dioxide
Sulfur dioxide (IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic activity and is produced as a by-product of copper extraction and the burning of sulfur- bearing fossil fuels. Structure and bonding SO2 is a bent molecule with ''C''2v symmetry point group. A valence bond theory approach considering just ''s'' and ''p'' orbitals would describe the bonding in terms of resonance between two resonance structures. The sulfur–oxygen bond has a bond order of 1.5. There is support for this simple approach that does not invoke ''d'' orbital participation. In terms of electron-counting formalism, the sulfur atom has an oxidation state of +4 and a formal charge of +1. Occurrence Sulfur dioxide is found on Earth and exists in very small concentrations and in the atmosphere at about 1 ppm. On other planets, ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Smiles Rearrangement
The Smiles rearrangement is an organic reaction and a rearrangement reaction named after British chemist Samuel Smiles. It is an intramolecular nucleophilic aromatic substitution of the type: where X in the arene compound can be a sulfone, a sulfide, an ether or any substituent capable of dislodging from the arene carrying a negative charge. The terminal functional group in the chain end Y is able to act as a strong nucleophile for instance an alcohol, amine or thiol. As in other nucleophilic aromatic substitutions the arene requires activation by an electron-withdrawing group preferably in the aromatic ortho position. In one modification called the Truce–Smiles rearrangement the incoming nucleophile is sufficiently strong that the arene does not require this additional activation, for example when the nucleophile is an organolithium. This reaction is exemplified by the conversion of an aryl sulfone into a sulfinic acid by action of ''n''-butyllithium: This particul ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Lithium Diisopropylamide
Lithium diisopropylamide (commonly abbreviated LDA) is a chemical compound with the molecular formula . It is used as a strong base and has been widely utilized due to its good solubility in non-polar organic solvents and non-nucleophilic nature. It is a colorless solid, but is usually generated and observed only in solution. It was first prepared by Hamell and Levine in 1950 along with several other hindered lithium diorganylamides to effect the deprotonation of esters at the α position without attack of the carbonyl group. Preparation and structure LDA is commonly formed by treating a cooled (0 to −78 °C) mixture of tetrahydrofuran and diisopropylamine with ''n''-butyllithium. When dissociated, the diisopropylamide anion can become protonated to form diisopropylamine. Diisopropylamine has a p''K''a value of 36. Therefore, its conjugate base is suitable for the deprotonation of compounds with greater acidity, importantly, such weakly acidic compounds (carbon acids) ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
