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Oxaphosphetane
An oxaphosphetane is a molecule containing a four-membered ring with one phosphorus, one oxygen and two carbon atoms. In a 1,2-oxaphosphetane phosphorus is bonded directly to oxygen, whereas a 1,3-oxaphosphetane has the phosphorus and oxygen atoms at opposite corners. 1,2-Oxaphosphetanes are rarely isolated but are important intermediates in the Wittig reaction and related reactions such as the Seyferth–Gilbert homologation and the Horner–Wadsworth–Emmons reaction. Edwin Vedejs's NMR studies first revealed the importance of oxaphosphetanes in the mechanism of the Wittig reaction in the 1970s. In 2005 the first isolation of 1,2-Oxaphosphetanes (typical Wittig intermediates) was reported. One of the compounds was characterized by X-ray crystallography and NMR. Although relatively stable, thermal decomposition of these oxaphosphetanes gave a phosphonium salt, which slowly dissociated to the Wittig reaction The Wittig reaction or Wittig olefination is a chemical reaction ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Wittig Reaction
The Wittig reaction or Wittig olefination is a chemical reaction of an aldehyde or ketone with a triphenyl phosphonium ylide called a Wittig reagent. Wittig reactions are most commonly used to convert aldehydes and ketones to alkenes. Most often, the Wittig reaction is used to introduce a methylene group using methylenetriphenylphosphorane (Ph3P=CH2). Using this reagent, even a sterically hindered ketone such as camphor can be converted to its methylene derivative. Reaction mechanism Mechanistic studies have focused on unstabilized ylides, because the intermediates can be followed by NMR spectroscopy. The existence and interconversion of the betaine (3a and 3b) is subject of ongoing research. For lithium-free Wittig reactions, studies support a concerted formation of the oxaphosphetane without intervention of a betaine. In particular, phosphonium ylides 1 react with carbonyl compounds 2 via a +2cycloaddition that is sometimes described as having π2s+π2a">sub>π2s+π2 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Horner–Wadsworth–Emmons Reaction
The Horner–Wadsworth–Emmons (HWE) reaction is a chemical reaction used in organic chemistry of stabilized phosphonate carbanions with aldehydes (or ketones) to produce predominantly E-alkenes. In 1958, Leopold Horner published a modified Wittig reaction using phosphonate-stabilized carbanions. William S. Wadsworth and William D. Emmons further defined the reaction. In contrast to phosphonium ylides used in the Wittig reaction, phosphonate-stabilized carbanions are more nucleophilic but less basic. Likewise, phosphonate-stabilized carbanions can be alkylated. Unlike phosphonium ylides, the dialkylphosphate salt byproduct is easily removed by aqueous extraction. Several reviews have been published. Reaction mechanism The Horner–Wadsworth–Emmons reaction begins with the deprotonation of the phosphonate to give the phosphonate carbanion 1. Nucleophilic addition of the carbanion onto the aldehyde 2 (or ketone) producing 3a or 3b is the rate-limiting step. If ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Edwin Vedejs
Edwin Vedejs () (; January 31, 1941 – December 2, 2017) was a Latvian-American professor of chemistry. In 1967, he joined the organic chemistry faculty at University of Wisconsin. He rose through the ranks during his 32 years at Wisconsin being named Helfaer Professor (1991–1996) and Robert M. Bock Professor (1997–1998). In 1999, he moved to the University of Michigan and served as the Moses Gomberg Collegiate Professor of Chemistry for the final 13 years of his tenure. He was elected a fellow of the American Chemical Society in 2011. After his retirement in 2011, the University of Michigan established the Edwin Vedejs Collegiate Professor of Chemistry Chair. Vedejs died on December 2, 2017, in Madison, Wisconsin. Early life and education Edwin "Ed" Vedejs was born in Riga, Latvia to Velta (nee Robežnieks) and Nikolajs Vedējs. Not long after his birth, the German occupation of Latvia during World War II occurred followed by the Soviet re-occupation of Latvia in 1944. These ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Seyferth–Gilbert Homologation
The Seyferth–Gilbert homologation is a chemical reaction of an aryl ketone 1 (or aldehyde) with dimethyl (diazomethyl)phosphonate 2 and potassium tert-butoxide to give substituted alkynes 3. Dimethyl (diazomethyl)phosphonate 2 is often called the Seyferth–Gilbert reagent. This reaction is called a ''Homologation reactions, homologation'' because the product has exactly one additional carbon more than the starting material. Reaction mechanism Deprotonation of the Seyferth–Gilbert reagent A gives an anion B, which reacts with the ketone to form the oxaphosphetane D. Elimination of dimethylphosphate E gives the vinyl group, vinyl diazo-intermediate Fa and Fb. The generation of nitrogen gas gives a vinyl group, vinyl carbene G, which via a 1,2-rearrangement, 1,2-migration forms the desired alkyne H. Bestmann modification The dimethyl (diazomethyl)phosphonate carbanion can be generated ''in situ'' from dimethyl-1-diazo-2-oxopropylphosphonate (also called the Ohira-Bestmann ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Phosphorus Heterocycles
Phosphorus is a chemical element; it has symbol P and atomic number 15. All elemental forms of phosphorus are highly reactive and are therefore never found in nature. They can nevertheless be prepared artificially, the two most common allotropes being white phosphorus and red phosphorus. With as its only stable isotope, phosphorus has an occurrence in Earth's crust of about 0.1%, generally as phosphate rock. A member of the pnictogen family, phosphorus readily forms a wide variety of organic and inorganic compounds, with as its main oxidation states +5, +3 and −3. The isolation of white phosphorus in 1669 by Hennig Brand marked the scientific community's first discovery since Antiquity of an element. The name phosphorus is a reference to the god of the Morning star in Greek mythology, inspired by the faint glow of white phosphorus when exposed to oxygen. This property is also at the origin of the term ''phosphorescence'', meaning glow after illumination, although white pho ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
X-ray Crystallography
X-ray crystallography is the experimental science of determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to Diffraction, diffract in specific directions. By measuring the angles and intensities of the X-ray diffraction, a crystallography, crystallographer can produce a three-dimensional picture of the density of electrons within the crystal and the positions of the atoms, as well as their chemical bonds, crystallographic disorder, and other information. X-ray crystallography has been fundamental in the development of many scientific fields. In its first decades of use, this method determined the size of atoms, the lengths and types of chemical bonds, and the atomic-scale differences between various materials, especially minerals and alloys. The method has also revealed the structure and function of many biological molecules, including vitamins, drugs, proteins and nucleic acids such as DNA. X-ray crystall ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Tetrahedron Letters
''Tetrahedron Letters'' is a weekly international journal for rapid publication of full original research papers in the field of organic chemistry. According to the ''Journal Citation Reports'', the journal has a 2022 impact factor of 1.8 Indexing ''Tetrahedron Letters'' is indexed in: References See also *''Tetrahedron In geometry, a tetrahedron (: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular Face (geometry), faces, six straight Edge (geometry), edges, and four vertex (geometry), vertices. The tet ...'' *'' Tetrahedron: Asymmetry'' Chemistry journals Weekly journals Academic journals established in 1959 Elsevier academic journals {{chem-journal-stub ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
The Journal Of Organic Chemistry
''The Journal of Organic Chemistry'', colloquially known as ''JOC'', is a peer-reviewed scientific journal for original contributions of fundamental research in all branches of theory and practice in organic and bioorganic chemistry. It is published by the publishing arm of the American Chemical Society, with 24 issues per year. According to the ''Journal Citation Reports'', the journal had a 2023 impact factor of 3.3 and it is the journal that received the most cites (100,091 in 2017) in the field of organic chemistry. According to Web of Knowledge (and as December 2012), eleven papers from the journal have received more than 1,000 citations, with the most cited paper having received 7,967 citations. The current editor-in-chief is Scott J. Miller from Yale University. Indexing ''J. Org. Chem.'' is currently indexed in: See also * Organic Letters *Organometallics ''Organometallics'' is a biweekly journal published by the American Chemical Society. Its area of focus is o ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Nuclear Magnetic Resonance Spectroscopy
Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy or magnetic resonance spectroscopy (MRS), is a Spectroscopy, spectroscopic technique based on re-orientation of Atomic nucleus, atomic nuclei with non-zero nuclear spins in an external magnetic field. This re-orientation occurs with absorption of electromagnetic radiation in the radio frequency region from roughly 4 to 900 MHz, which depends on the Isotope, isotopic nature of the nucleus and increases proportionally to the strength of the external magnetic field. Notably, the resonance frequency of each NMR-active nucleus depends on its chemical environment. As a result, NMR spectra provide information about individual functional groups present in the sample, as well as about connections between nearby nuclei in the same molecule. As the NMR spectra are unique or highly characteristic to individual compounds and functional groups, NMR spectroscopy is one of the most important methods to identify ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ball-and-stick Model
In chemistry, the ball-and-stick model is a molecular model of a chemical substance which displays both the Molecular geometry, three-dimensional position of the atoms and the chemical bond, bonds between them. The atoms are typically represented by sphere (geometry), spheres, connected by rods which represent the bonds. Double bond, Double and triple bonds are usually represented by two or three curved rods, respectively, or alternately by correctly positioned sticks for the sigma bond, sigma and pi bonds. In a good model, the angles between the rods should be the same as the Bond angle, angles between the bonds, and the distances between the centers of the spheres should be proportional to the distances between the corresponding atomic nucleus, atomic nuclei. The chemical element of each atom is often indicated by the sphere's color. In a ball-and-stick model, the radius of the spheres is usually much smaller than the rod lengths, in order to provide a clearer view of the atoms ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chemical Society Reviews
''Chemical Society Reviews'' is a biweekly peer-reviewed scientific journal published by the Royal Society of Chemistry, for review articles on topics of current interest in chemistry. Its predecessors were ''Quarterly Reviews, Chemical Society'' (1947–1971) and ''Royal Institute of Chemistry, Reviews'' (1968–1971); it maintained its current title since 1972. According to the ''Journal Citation Reports'', the journal has a 2023 impact factor of 40.4. The current editor-in-chief (chair of editorial board) is Jennifer Love (University of Calgary). ''Chemical Society Reviews'' publishes occasional themed issues on new and emerging areas of research in the chemical sciences. These issues are edited by a guest editor who is a specialist in their field. Since 2005, ''Chemical Society Reviews'' has published reviews on topics of broad appeal, termed "social interest" reviews, such as articles on art conservation, forensics, and automotive fuels. The journal is abstracted and indexed ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
