- Catalytic Enantioselective Synthesis of 1,4-Keto-Alkenylboronate Esters and 1,4-Dicarbonyls
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A catalytic enantioselective method for the synthesis of 1,4-keto-alkenylboronate esters by a rhodium-catalyzed conjugate addition pathway is disclosed. A variety of novel, bench-stable alkenyl gem-diboronate esters are synthesized. These easily accessible reagents react smoothly with a collection of cyclic α,β-unsaturated ketones, generating a new C?C bond and stereocenter. Products are isolated in up to 99 % yield with greater than 20:1 E/Z and greater than 99:1 e.r. Mechanistic studies show the site-selectivity of transmetalation and reactivity is ligand dependent. The utility of the approach is highlighted by gram-scale synthesis of enantioenriched cyclic 1,4-diketones, and stereoselective transformations of the products by hydrogenation, allylation, and isomerization.
- Liang, Michael Z.,Meek, Simon J.
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supporting information
p. 14234 - 14239
(2019/08/30)
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- Discovery and Computational Rationalization of Diminishing Alternation in [n]Dendralenes
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The [n]dendralenes are a family of acyclic hydrocarbons which, by virtue of their ability to rapidly generate structural complexity, have attracted significant recent synthetic attention. [3]Dendralene through [8]dendralene have been previously prepared but no higher member of the family has been reported to date. Here, we describe the first chemical syntheses of the "higher" dendralenes, [9]dendralene through [12]dendralene. We also report a detailed investigation into the spectroscopic properties and chemical reactivity of the complete family of fundamental hydrocarbons, [3]dendralene to [12]dendralene. These studies reveal the first case of diminishing alternation in behavior in a series of related structures. We also report a comprehensive series of computational studies, which trace this dampening oscillatory effect in both spectroscopic measurements and chemical reactivity to conformational preferences.
- Saglam, Mehmet F.,Fallon, Thomas,Paddon-Row, Michael N.,Sherburn, Michael S.
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supporting information
p. 1022 - 1032
(2016/02/05)
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- Method for producing 1,1-dibromo-1-fluoroethane
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The present invention addresses the problem of providing a production method which enables 1,1-dibromo-1-fluoroethane to be produced in a simple and sustained manner. The present invention provides a method for producing 1,1-dibromo-1-fluoroethane, said method comprising step A of reacting 1,1-dibromoethylene with hydrogen fluoride to produce 1,1-dibromo-1-fluoroethane.
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Paragraph 0120; 0121
(2016/11/21)
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- METHOD FOR PRODUCING 1,1-DIBROMO-1-FLUOROETHANE
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An object of the present invention is to provide a production method that makes it possible to produce 1,1-dibromo-1-fluoroethane easily and sustainably. The present invention provides a method for producing 1,1-dibromo-1-fluoroethane, the method comprising step A of reacting 1,1-dibromoethylene with hydrogen fluoride to obtain 1,1-dibromo-1-fluoroethane.
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Paragraph 0087
(2016/08/29)
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- METHOD FOR MANUFACTURING 1,1,2-TRIBROMOETHANE
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PROBLEM TO BE SOLVED: To provide a method for manufacturing 1,1,2-tribromoethane at low cost and high yield. SOLUTION: There is provided a method for manufacturing 1,1,2-tribromoethane, including a process A of brominating 1,1,2-trihaloethane represented by the formula (1), where X1, X2 and X3 represent a chlorine atom or a bromine atom, however at least one of X1, X2 and X3 is a chlorine atom, to obtain 1,1,2-tribromoethane. COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0071
(2016/10/07)
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- PRODUCTION METHOD OF MONOFLUOROETHYLENE COMPOUND
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PROBLEM TO BE SOLVED: To provide a synthesis method capable of giving a monofluoroethylene compound with a difluoroethylene compound as a material, under mild conditions, at ease and with high selectivity. SOLUTION: A production method of a monofluoroethylene compound represented by the formulas (1-1), (1-2) or (1-3) comprises a step of a difluoroethylene compound represented by the formulas (2-1), (2-2) or (2-3) with a compound represented by the formula (3): BX3, to obtain a monofluoroethylene compound represented by the formulas (1-1), (1-2) or (1-3). [R1 and R2 may be identically or differently H, an alkyl group, or a phenyl group which may be substituted with one or more substituent groups, or may be linked to each other to form a carbocyclic ring; and X is Cl or Br.] COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0041
(2016/12/22)
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- PYRIDINE ANCHORS FOR HMG-COA REDUCTASE INHIBITORS
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Compounds which are useful as inhibitors of cholesterol biosynthesis and thus as hypocholesterolemic agents are provided which have a quinoline or a pyridine anchor attached by means of a linker to a binding domain sidechain, which compounds inhibit the e
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- SULFUR-CONTAINING HMG-COA REDUCTASE INHIBITORS
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Novel sulfur-containing compounds which inhibit the activity of 3-hydroxy-3-methylglutaryl-coenzyme A (HMG-CoA) reductase, having a sulfur-containing side-chain bonded to a hydrophobic anchor group through an acetylenic or ethylenic linkage. Pharmaceutica
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- PRODUCTION OF 1,1,1-TRIHALOGENO-2-ALKANOLS AND SOME OF THEIR PROPERTIES
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The reaction of acyclic and carbocyclic carbonyl compounds with haloforms was studied in liquid ammonia and dimethylformamide in the presence of basic catalysts (t-BuOK, KOH).As a result of the reaction 1,1,1-trihalogeno-2-alkanols were obtained.They were used for the synthesis of 1,1,1-trihalogeno-2-methoxyalkanes, 1,1-dibromoalkenes, 1,1-dichloro-2-methoxyalkenes, and alkyl mono- and dichloromethyl ketones.
- Bal'on, Ya. G.,Shul'man, M. D.,Vakulenko, L. I.
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p. 1231 - 1237
(2007/10/02)
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- Manufacture of gamma halogen substituted adducts
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Halogen-substituted olefin addition compounds that contain a carbonyl group are formed by oxidatively adducting an olefin and a carbonyl compound such as a ketone, aldehyde, or ester. The method consists of reacting the olefin and the carbonyl component, in solution, with an oxidizing ion of manganese, cerium or vanadium in the presence of fluoride, chloride or bromide ion. This ionic component is incorporated in the adduct and appears on the olefin-derived carbon atom gamma to the carbonyl group. The gamma halogen substituted adducts are readily converted to cyclopropane derivatives, including pyrethroid intermediate compounds.
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