Nazarov Cyclization
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Nazarov Cyclization
The Nazarov cyclization reaction (often referred to as simply the Nazarov cyclization) is a chemical reaction used in organic chemistry for the synthesis of cyclopentenones. The reaction is typically divided into ''classical'' and ''modern'' variants, depending on the reagents and substrates employed. It was originally discovered by Ivan Nikolaevich Nazarov (1906–1957) in 1941 while studying the rearrangements of allyl vinyl ketones. As originally described, the Nazarov cyclization involves the activation of a divinyl ketone using a stoichiometric Lewis acid or protic acid promoter. The key step of the reaction mechanism involves a cationic 4π- electrocyclic ring closure which forms the cyclopentenone product (See Mechanism below). As the reaction has been developed, variants involving substrates other than divinyl ketones and promoters other than Lewis acids have been subsumed under the name Nazarov cyclization provided that they follow a similar mechanistic pathway. T ...
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Ivan Nikolaevich Nazarov
Ivan Nikolaevich Nazarov (russian: Иван Николаевич Назаров; 12 June 1906 – 30 July 1957) was an organic chemist from the former USSR. Ivan Nikolaevich Nazarov has born on June 12, 1906. He was an organic chemist who started his scientific activities in 1931 at Leningrad State University. Nazarov published more than 300 scientific papers. In 1946, he was elected as a Corresponding Member of the Academy of Sciences of the USSR, and in 1953 he became an academician. Nazarov died 30 July 1957. The Nazarov cyclization reaction The Nazarov cyclization reaction (often referred to as simply the Nazarov cyclization) is a chemical reaction used in organic chemistry for the synthesis of cyclopentenones. The reaction is typically divided into ''classical'' and ''modern'' var ... is named after him. References * * {{DEFAULTSORT:Nazarov, Ivan 1906 births 1957 deaths Soviet chemists 20th-century chemists Russian chemists Full Members of the USSR Academy ...
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Aflatoxin
Aflatoxins are various poisonous carcinogens and mutagens that are produced by certain molds, particularly ''Aspergillus'' species. The fungi grow in soil, decaying vegetation and various staple foodstuffs and commodities such as hay, sweetcorn, wheat, millet, sorghum, cassava, rice, chili peppers, cottonseed, peanuts, tree nuts, sesame seeds, sunflower seeds, and various spices. In short, the relevant fungi grow on almost any crop or food. When such contaminated food is processed or consumed, the aflatoxins enter the general food supply. They have been found in both pet and human foods, as well as in feedstocks for agricultural animals. Animals fed contaminated food can pass aflatoxin transformation products into eggs, milk products, and meat. For example, contaminated poultry feed is the suspected source of aflatoxin-contaminated chicken meat and eggs in Pakistan. Children are particularly affected by aflatoxin exposure, which is associated with stunted growth, delayed de ...
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Elimination Reaction
An elimination reaction is a type of organic reaction in which two substituents are removed from a molecule in either a one- or two-step mechanism. The one-step mechanism is known as the E2 reaction, and the two-step mechanism is known as the E1 reaction. The numbers refer not to the number of steps in the mechanism, but rather to the kinetics of the reaction: E2 is bimolecular (second-order) while E1 is unimolecular (first-order). In cases where the molecule is able to stabilize an anion but possesses a poor leaving group, a third type of reaction, E1CB, exists. Finally, the pyrolysis of xanthate and acetate esters proceed through an "internal" elimination mechanism, the Ei mechanism. E2 mechanism The E2 mechanism, where E2 stands for bimolecular elimination, involves a one-step mechanism in which ''carbon-hydrogen'' and ''carbon-halogen'' bonds break to form a double bond (''C=C Pi bond''). The specifics of the reaction are as follows: * E2 is a single step elimination, ...
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Conrotatory And Disrotatory
An electrocyclic reaction can either be classified as conrotatory or disrotatory based on the rotation at each end of the molecule. In conrotatory mode, both atomic orbitals of the end groups turn in the same direction (such as both atomic orbitals rotating clockwise or counter-clockwise). In disrotatory mode, the atomic orbitals of the end groups turn in opposite directions (one atomic orbital turns clockwise and the other counter-clockwise). The cis/trans geometry of the final product is directly decided by the difference between conrotation and disrotation. Determining whether a particular reaction is conrotatory or disrotatory can be accomplished by examining the molecular orbitals of each molecule and through a set of rules. Only two pieces of information are required to determine conrotation or disrotation using the set of rules: how many electrons are in the pi-system and whether the reaction is induced by heat or by light. This set of rules can also be derived from an ana ...
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Pentadienyl
In organic chemistry, pentadienyl refers to the organic radical, anion, or cation with the formula , where ''z'' = 0, −1, +1, respectively. Organometallic chemistry In organometallic chemistry, the pentadienyl anion is a ligand, the acyclic analogue of the more-common cyclopentadienyl anion. The pentadienyl anion is generated by deprotonation of pentadiene. A number of complexes are known, including bis(pentadienyl) iron, , the "open" analog of ferrocene. Only few pentadienyl complexes feature simple ligands. More common is the dimethyl derivative 2,4-. Additionally, many pentadienyl ligands are cyclic, being derived from the addition of hydride to ''η''6-arene complexes or hydride abstraction from cyclohexadiene complexes. The first pentadienyl complex to be reported was derived from protonolysis of a complex of pentadienol: :Fe(C5H7OH)(CO)3 + H+ -> e(C5H7)(CO)3 + H2O Treatment of this cation with sodium borohydride gives the pentadiene complex: : e(C5H7)(CO)3 + H- -> Fe(C5H ...
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Ketone
In organic chemistry, a ketone is a functional group with the structure R–C(=O)–R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group –C(=O)– (which contains a carbon-oxygen double bond C=O). The simplest ketone is acetone (where R and R' is methyl), with the formula . Many ketones are of great importance in biology and in industry. Examples include many sugars (ketoses), many steroids (e.g., testosterone), and the solvent acetone. Nomenclature and etymology The word ''ketone'' is derived from ''Aketon'', an old German word for ''acetone''. According to the rules of IUPAC nomenclature, ketone names are derived by changing the suffix ''-ane'' of the parent alkane to ''-anone''. Typically, the position of the carbonyl group is denoted by a number, but traditional nonsystematic names are still generally used for the most important ketones, for example acetone and benzophenone. These nonsystematic names are considere ...
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Electrocyclic Reaction
In organic chemistry, an electrocyclic reaction is a type of pericyclic rearrangement where the net result is one pi bond being converted into one sigma bond or vice versa. These reactions are usually categorized by the following criteria: * Reactions can be either photochemical or thermal. * Reactions can be either ring-opening or ring-closing (electrocyclization). * Depending on the type of reaction (photochemical or thermal) and the number of pi electrons, the reaction can happen through either a conrotatory or disrotatory mechanism. * The type of rotation determines whether the cis or trans isomer of the product will be formed. Classical examples The Nazarov cyclization reaction is a named electrocyclic reaction converting divinylketones to cyclopentenones. A classic example is the thermal ring-opening reaction of 3,4-dimethylcyclobutene. The cis isomer exclusively yields whereas the trans isomer gives the trans,trans diene: This reaction course can be explained in a sim ...
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Intramolecular Reaction
Intramolecular in chemistry describes a process or characteristic limited within the structure of a single molecule, a property or phenomenon limited to the extent of a single molecule. Examples * intramolecular hydride transfer (transfer of a hydride ion from one part to another within the same molecule) * intramolecular hydrogen bond (a hydrogen bond formed between two functional groups of the same molecule) *cyclization of ω-haloalkylamines and alcohols to form the corresponding saturated nitrogen and oxygen heterocycles, respectively (an SN2 reaction within the same molecule) In intramolecular organic reactions, two reaction sites are contained within a single molecule. This creates a very high effective concentration (resulting in high reaction rates), and, therefore, many intramolecular reactions that would not occur as an intermolecular reaction between two compounds take place. Examples of intramolecular reactions are the Smiles rearrangement, the Dieckmann condensation ...
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Charles Shoppee
Charles William Shoppee FAA FRS (1904–1994) was a British-born organic chemist who performed major research into steroids. He was Professor of Chemistry at the University of Wales (1946–1956) and Professor of Organic Chemistry at the University of Sydney (1956–1969). Mander, Lewis N.'Charles William Shoppee 1904-1994' 5 November 2003, Historical Records of Australian Science, vol. 14, no. 4, pp. 509-528.Professor Charles William Shoppee - Elected (FAA) 1958
Australian Academy of Science
Shoppee, Charles William, (FAA, FRS) (1904-1994)
trove.nla.gov.au
The short cit ...
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Organic Reactions
Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic reactions, rearrangement reactions, photochemical reactions and redox reactions. In organic synthesis, organic reactions are used in the construction of new organic molecules. The production of many man-made chemicals such as drugs, plastics, food additives, fabrics depend on organic reactions. The oldest organic reactions are combustion of organic fuels and saponification of fats to make soap. Modern organic chemistry starts with the Wöhler synthesis in 1828. In the history of the Nobel Prize in Chemistry awards have been given for the invention of specific organic reactions such as the Grignard reaction in 1912, the Diels-Alder reaction in 1950, the Wittig reaction in 1979 and olefin metathesis in 2005. Classifications Organic chemistry has a strong tradition of naming a specific reac ...
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Synthesis (journal)
''Synthesis'' is a scientific journal published from 1969 to the present day by Thieme Medical Publishers, Thieme. Its stated purpose is the "advancement of the science of synthetic chemistry". From August 2006, selected articles are offered free of charge. The impact factor of this journal is 2.867 (2018).Journal Citation Reports, 2018 References Chemistry journals English-language journals Thieme academic journals {{chem-journal-stub ...
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