Iodolactonization
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Iodolactonization
Iodolactonization (or, more generally, halolactonization) is an organic reaction that forms a ring (the lactone) by the addition of an oxygen and iodine across a carbon-carbon double bond. It is an intramolecular variant of the halohydrin synthesis reaction. The reaction was first reported by M. J. Bougalt in 1904 and has since become one of the most effective ways to synthesize lactones. Strengths of the reaction include the mild conditions and incorporation of the versatile iodine atom into the product. : Iodolactonization has been used in the synthesis of many natural products including those with medicinal applications such as vernolepin and vernomenin, two compounds used in tumor growth inhibition, and vibralactone, a pancreatic lipase inhibitor. Iodolactonization has also been used by Elias James Corey to synthesize numerous prostaglandins. History Sandra's report of iodolactonization represented the first example of a reliable lactonization that could be used in many dif ...
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Bromolactonization
Iodolactonization (or, more generally, halolactonization) is an organic reaction that forms a ring (the lactone) by the addition of an oxygen and iodine across a carbon-carbon double bond. It is an intramolecular reaction, intramolecular variant of the halohydrin synthesis reaction. The reaction was first reported by M. J. Bougalt in 1904 and has since become one of the most effective ways to synthesize lactones. Strengths of the reaction include the mild conditions and incorporation of the versatile iodine atom into the product. : Iodolactonization has been used in the synthesis of many natural products including those with medicinal applications such as vernolepin and vernomenin, two compounds used in tumor growth inhibition, and vibralactone, a pancreatic lipase inhibitor. Iodolactonization has also been used by Elias James Corey to synthesize numerous prostaglandins. History Sandra's report of iodolactonization represented the first example of a reliable lactonization that cou ...
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Elias James Corey
Elias James Corey (born July 12, 1928) is an American organic chemistry, organic chemist. In 1990, he won the Nobel Prize in Chemistry "for his development of the theory and methodology of organic synthesis", specifically retrosynthetic analysis. Regarded by many as one of the greatest living chemists, he has developed numerous synthetic reagents, methodologies and total syntheses and has advanced the science of organic synthesis considerably. Biography E.J. Corey (the surname was anglicized from Levantine Arabic ''Khoury'', meaning ''priest'') was born to Lebanese Greek Orthodox Christians, Lebanese Greek Orthodox Christian immigrants Fatima (née Hasham) and Elias Corey in Methuen, Massachusetts, north of Boston. His mother changed his name from William to "Elias" to honor his father, who died eighteen months after Corey's birth. His widowed mother, brother, two sisters, aunt and uncle all lived together in a spacious house, struggling through the Great Depression. As a young b ...
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Lactone
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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Thermodynamic
Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of thermodynamics which convey a quantitative description using measurable macroscopic physical quantities, but may be explained in terms of microscopic constituents by statistical mechanics. Thermodynamics applies to a wide variety of topics in science and engineering, especially physical chemistry, biochemistry, chemical engineering and mechanical engineering, but also in other complex fields such as meteorology. Historically, thermodynamics developed out of a desire to increase the efficiency of early steam engines, particularly through the work of French physicist Sadi Carnot (1824) who believed that engine efficiency was the key that could help France win the Napoleonic Wars. Scots-Irish physicist Lord Kelvin was the first to formulate a co ...
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Samuel Danishefsky
Samuel J. Danishefsky (born March 10, 1936) is an American chemist working as a professor at both Columbia University and the Memorial Sloan-Kettering Cancer Center in New York City. Birth and education Samuel J. Danishefsky was born in 1936 in the United States. He completed his B.S. from Yeshiva University in 1956. He earned his Ph.D. in chemistry from Harvard University in 1962 with Peter Yates (chemist), Peter Yates, which partially overlapped with a National Institutes of Health postdoctoral fellowship in the laboratory of Gilbert Stork at Columbia University. Academic career After completing his PhD, he became professor at the University of Pittsburgh, where he eventually attained the rank of University Professor and taught until 1979. From 1979 to 1993, he was a professor at Yale University, where he rose to the rank of Sterling Professor of Chemistry. By 1991 he was sharing his time with Memorial Sloan-Kettering Cancer Center as director of the Laboratory for Cancer Re ...
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Total Syntheses
Total synthesis is the complete chemical synthesis of a complex molecule, often a natural product, from simple, commercially-available precursors. It usually refers to a process not involving the aid of biological processes, which distinguishes it from semisynthesis. Syntheses may sometimes conclude at a precursor with further known synthetic pathways to a target molecule, in which case it is known as a formal synthesis. Total synthesis target molecules can be natural products, medicinally-important active ingredients, known intermediates, or molecules of theoretical interest. Total synthesis targets can also be organometallic or inorganic, though these are rarely encountered. Total synthesis projects often require a wide diversity of reactions and reagents, and subsequently requires broad chemical knowledge and training to be successful. Often, the aim is to discover a new route of synthesis for a target molecule for which there already exist known routes. Sometimes, however, n ...
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Lipid
Lipids are a broad group of naturally-occurring molecules which includes fats, waxes, sterols, fat-soluble vitamins (such as vitamins A, D, E and K), monoglycerides, diglycerides, phospholipids, and others. The functions of lipids include storing energy, signaling, and acting as structural components of cell membranes. Lipids have applications in the cosmetic and food industries, and in nanotechnology. Lipids may be broadly defined as hydrophobic or amphiphilic small molecules; the amphiphilic nature of some lipids allows them to form structures such as vesicles, multilamellar/unilamellar liposomes, or membranes in an aqueous environment. Biological lipids originate entirely or in part from two distinct types of biochemical subunits or "building-blocks": ketoacyl and isoprene groups. Using this approach, lipids may be divided into eight categories: fatty acyls, glycerolipids, glycerophospholipids, sphingolipids, saccharolipids, and polyketides (derived from condensati ...
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Baldwin's Rules
Baldwin's rules in organic chemistry are a series of guidelines outlining the relative favorabilities of ring closure reactions in alicyclic compounds. They were first proposed by Jack Baldwin in 1976. Baldwin's rules discuss the relative rates of ring closures of these various types. These terms are not meant to describe the absolute probability that a reaction will or will not take place, rather they are used in a relative sense. A reaction that is disfavoured (slow) does not have a rate that is able to compete effectively with an alternative reaction that is favoured (fast). However, the disfavoured product may be observed, if no alternate reactions are more favoured. The rules classify ring closures in three ways: *the number of atoms in the newly formed ring *into ''exo'' and ''endo'' ring closures, depending whether the bond broken during the ring closure is inside (''endo'') or outside (''exo'') the ring that is being formed *into ''tet'', ''trig'' and ''dig'' geometry of ...
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