- Copper(II)-catalyzed ether synthesis from aliphatic alcohols and potassium organotrifluoroborate salts
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(Matrix presented) A protocol for the copper(II)-catalyzed etherification of aliphatic alcohols under mild and essentially neutral conditions is described. Air- and moisture-stable potassium alkenyl- and aryltrifluoroborate salts undergo cross-coupling with a variety of aliphatic primary and secondary alcohols and phenols, and are tolerant of a range of functional groups. The optimized conditions utilize catalytic copper(II) acetate with 4-(dimethylamino)pyridine as ligand in the presence of 4 A molecular sieves under an atmosphere of oxygen.
- Quach, Tan D.,Batey, Robert A.
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Read Online
- Preparation method and application of propyne aryl ether compound
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The invention particularly relates to a method for preparing propyne aryl ether compounds from aryl phenol, halogenated propyne and derivatives of the halogenated propyne, and belongs to the technical field of preparation of the propyne aryl ether compoun
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Paragraph 0043-0044
(2021/08/28)
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- Copper-catalyzed intramolecular carbotrifluoromethylation of alkynes for the construction of trifluoromethylated heterocycles
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A mild and efficient copper-catalyzed intramolecular carbotrifluoromethylation of alkynes has been achieved in the presence of Togni reagent as trifluoromethylating reagent. The reaction tolerates a range of substrates to give a group of trifluoromethylated heterocycles with high selectivities. A plausible mechanism was proposed on the basis of experimental results. And the Togni award goes to Copper-catalyzed intramolecular carbotrifluoromethylation of alkynes is carried out with a Togni reagent as the trifluoromethylating reagent (see scheme). Various trifluoromethylated heterocycles are synthesized in moderate to good yields. Moreover, a range of common functional groups is tolerated under the reaction conditions.
- Wang, Yanan,Jiang, Min,Liu, Jin-Tao
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supporting information
p. 15315 - 15319
(2016/02/18)
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- Selective formation of six-membered oxa- and carbocycles by the In(III)-activated ring closure of acetylenic substrates
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Fifteen examples are disclosed of efficient In(III)-catalyzed six-membered ring closure leading to bi-, tri-, and tetracyclic products.
- Qiu, Wen-Wei,Surendra, Karavadhi,Yin, Liang,Corey
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supporting information; experimental part
p. 5893 - 5895
(2011/12/16)
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- Gold nanoparticles supported on TiO2 catalyse the cycloisomerisation/oxidative dimerisation of aryl propargyl ethers
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Gold nanoparticles supported on TiO2 (~1%) catalyse in high yields the selective cycloisomerisation of aryl propargyl ethers into the corresponding 2H-chromenes, under heterogeneous conditions. 2H,2′H-3, 3′-Bichromenes resulting from a catalytic oxidative dimerization pathway are also formed as by-products. The Royal Society of Chemistry 2011.
- Efe, Christina,Lykakis, Ioannis N.,Stratakis, Manolis
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supporting information; experimental part
p. 803 - 805
(2011/04/12)
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- Ph3PAuNTf2 as a superior catalyst for the selective synthesis of 2H-chromenes: Application to the concise synthesis of benzopyran natural products
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Ph3PAuNTf2 (≈1 mol-%) catalyzes the selective cycloisomerization of substituted aryl propargyl ethers into 2H-chromenes in excellent yields. Benzofuran byproducts are formed only in the case of electron-deficient arenes, in up to 7% relative yield. The Ph 3PAuNTf2-catalyzed cyclization of aryl propargyl ethers was applied as a key step to the concise synthesis of the naturally occurring benzopyrans seselin, xanthyletin, precocenes I and II, 8-(3′,3′- dimethylallyl)wenteria chromene, and 2,2-dimethyl-8-prenylchromene-6-propenoic acid. Ph3PAuNTf2 is a general, highly efficient, and product-selective catalyst for the clean synthesis of 2H-chromenes from the cycloisomerization of aryl propargyl ethers.The Ph3PAuNTf 2-catalyzed cyclization was applied as a key step in the synthesis of several benzopyran-bearing naturally occurring substances. Copyright
- Lykakis, Ioannis N.,Efe, Christina,Gryparis, Charis,Stratakis, Manolis
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supporting information; experimental part
p. 2334 - 2338
(2011/06/20)
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- 11C-C bond formation by palladium-mediated cross-coupling of alkenylzirconocenes with [11C]methyl iodide
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A novel 11C-C bond formation based on the palladium-mediated cross-coupling reaction of alkenylzirconocenes with [11C]methyl iodide is described. The conversion of internal alkynes into the corresponding alkenylzirconocenes followed by transmetalation with Pd(PPh3) 4 and subsequent cross-coupling with [11C]methyl iodide gave several 11C-labelled α,α′-dimethyl-substituted alkenes. The palladium complex Pd(PPh3)4 proved to be superior to Pt(PPh3)4 or Ni(PPh3)4 as transition metal complex. The scope and limitations of the novel palladium-mediated cross-coupling reaction of alkenylzirconocenes with [ 11C]methyl iodide were tested with various internal alkynes. After heating at 60°C for 6 min radiochemical yields of up to 75% (based upon [11C]methyl iodide) could be achieved. Copyright
- Wuest, Frank R.,Berndt, Mathias
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- ALKYNYL CONTAINING HYDROXAMIC ACID DERIVATIVES, THEIR PREPARATION AND THEIR USE AS MATRIX METALLOPROTEINASE (MMP) INHIBITORS / TNF-ALPHA CONVERTING ENZYME (TACE) INHIBITORS
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Compounds of the formula:useful in the treatment of arthritis, tumor metastasis, tissue ulceration, abnormal wound healing, periodontal disease, bone disease, diabetes (insulin resistance) and HIV infection.
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Page/Page column 35
(2010/02/14)
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- ACETYLENIC ARYL SULFONAMIDE AND PHOSPHINIC ACID AMIDE HYDROXAMIC ACID TACE INHIBITORS
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Hydroxamic acids having formula (B) wherein the variables are as defined herein, are useful in treating disease conditions mediated by TNF- alpha such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple sclerosis, Crohn's d
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- Rapid methylation of terminal acetylenes by the Stille coupling of methyl iodide with alkynyltributylstannanes: A general protocol potentially useful for the synthesis of short-lived 11CH3-labeled PET tracers with a 1-propynyl group
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The Pd(0)-mediated rapid coupling (trapping) reaction of methyl iodide with an excess amount of alkynyltributyl-stannane has been developed with the aim to incorporate a short-lived 11C-labeled methyl group into biologically active organic compounds with a 1-propynyl structural unit.
- Hosoya, Takamitsu,Wakao, Masahiro,Kondo, Yurie,Doi, Hisashi,Suzuki, Masaaki
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- ACETYLENIC SULFONAMIDE THIOL TACE INHIBITORS
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Compounds of formula (B): (1a), or (1b), (1c) are provided wherein the variables are as defined herein which are useful in disease conditions mediated by TNF- alpha , such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple
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- HETEROARYL ACETYLENIC SULFONAMIDE AND PHOSPHINIC ACID AMIDE HYDROXAMIC ACID TACE INHIBITORS
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Compounds of formula (I) are useful in treating disease conditions mediated by TNF- alpha such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple sclerosis, Crohn's disease and degenerative cartilage loss.
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- ACETYLENIC ALPHA-AMINO ACID-BASED SULFONAMIDE HYDROXAMIC ACID TACE INHIBITORS
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Compound of the formula (B) are useful in treating disease conditions mediated by TNF- alpha , such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple sclerosis, Crohn's disease and degenerative cartilage loss.
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- 2, 3, 4, 5-TETRAHYDRO-1H-[1, 4] BENZODIAZEPINE-3-HYDROXAMIC ACIDS AS MATRIX METALLOPROTEINASE INHIBITORS
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Compounds having formula (1) are useful in treating disease conditions mediated by matrix metalloproteinases and TACE, such as tumor growth, osteoarthritis, rheumatoid arthritis and degenerative cartilage loss.
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- 2,3,4,5-tetrahydro-1H-(1,4)benzodiazepine-3-hydroxamic acids
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Compounds having the following formula: ? are useful in treating disease conditions mediated by matrix metalloproteinases and TACE, such as tumor growth, osteoarthritis, rheumatoid arthritis and degenerative cartilage loss.
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- Preparation and use of acetylenic ortho-sulfonamido and phosphinic acid amido bicyclic heteroaryl hydroxamic acids as TACE inhibitors
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Compounds of the formula which are useful in disease conditions mediated by TNF-α, such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple sclerosis, Crohn's disease and degenerative cartilage loss.
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(2010/01/31)
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- ACETYLENIC ORTHO-SULFONAMIDO AND PHOSPHINIC ACID AMIDO BICYCLIC HETEROARYL HYDROXAMIC ACIDS AS TACE INHIBITORS
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Compounds of the formula are provided wherein P and Q are provided that when P is Q is and vice versa; which are useful in disease conditions mediated by TNF- alpha , such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple sclerosis, Crohn's disease and degenerative cartilage loss.
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- Alkynyl containing hydroxamic acid compounds as matrix metalloproteinase/tace inhibitors
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Compounds of the formula: useful in the treatment of arthritis, tumor metastasis, tissue ulceration, abnormal wound healing, periodontal disease, bone disease, diabetes (insulin resistance) and HIV infection.
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- Acetylenic aryl sulfonamide and phosphinic acid amide hydroxamic acid TACE inhibitors
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Hydroxamic acids having the formula are useful in treating disease conditions mediated by TNF-α, such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple sclerosis, Crohn's disease and degenerative cartilage loss.
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- Acetylenic sulfonamide thiol tace inhibitors
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The compounds of formula B: which are useful in disease conditions mediated by TNF-α, such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple sclerosis, Crohn's disease and degenerative cartilage loss
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- Acetylenic β-sulfonamido and phosphinic acid amide hydroxamic acid TACE inhibitors
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The invention discloses hydroxamide acids of the formula: STR1which are useful in treating disease conditions mediated by TNF-α, such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple sclerosis, Crohn''s disease and degen
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- Heteroaryl acetylenic sulfonamide and phosphinic acid amide hydroxamic acid tace inhibitors
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Compounds of the formula: are useful in treating disease conditions mediated by TNF-α such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple sclerosis, Crohn's disease and degenerative cartilage loss.
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- Acetylenic α-amino acid-based sulfonamide hydroxamic acid tace inhibitors
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Compounds of the formula: are useful in treating disease conditions mediated by TNF-α, such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple sclerosis, Crohn's disease and degenerative cartilage loss.
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- Alkyliron and Alkylcobalt Reagents, VII. - On the Substitution of the Halogen of Alkenyl Chlorides, Alkenyl Fluorides, and Alkynyl Halides by Reagents of the Type R4MLi2 (M = Fe, Co)
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Me4FeLi2 and Me4CoLi2, which are favourable reagents for the substitution of Br in alkenyl bromides, also proved to be favourable for the substitution of the halogen in alkenyl chlorides (yields 68-99 percent; nearly complete retention of configuration in the case of Me4FeLi2), β-fluorostyrene (best yield 92 percent), and 1-fluoronaphthalene (best yield 47 percent).Me4FeLi2 differentiates between various alkenyl chlorides in 1:1 competition experiments better than Me4CoLi2 and is the optimal reagent for the substitution of halogen in 1-chloro-2-phenylethyne (12), 1-bromo-2-phenylethyne (13), and 1-chloro-3-phenoxypropyne (15) by methyl (yields 70, 46, and 80 percent, respectively).Substitution of the halogen in 12 by the n-butyl, n-octyl, and phenyl residue is better achieved by the catalytic systems RMgBr + 2.5 mol percent FeCl2 (R = nBu, nOct, Ph; yields 75, 63, and 96 percent, respectively) than by the reagents nBu4FeLi2, nBu4Fe(MgBr)2, nOct4Fe(MgBr)2, or Ph4Fe(MgBr)2 (yields 18-28 percent). Key Words: Iron, organo complexes / Cobalt, organo complexes
- Kauffmann, Thomas,Saelker, Reiner,Voss, Karl-Uwe
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p. 1447 - 1452
(2007/10/02)
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- Mercury in Organic Chemistry. 26. Synthesis of Heterocycles via Intramolecular Solvomercuration of Aryl Acetylenes
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A number of ortho substituted aryl acetylenes, o-CH3XC6H4YCCR (X=O, S, CO2; Y=-, CO), have been observed to undergo facile intramolecular solvomercuration with mercuric acetate in acetic acid to afford the corresponding benzofuran, benzothiophene, isocoumarin, and chromone organomercuric chlorides, after aqueous sodium chloride workup.The aryl acetylenes m-XC6H4YCH2CCR (X=H, Y=O, R=CH3; X=CH3O, Y=CH2, R=n-C3H7) undergo similar cyclizations to yield mercurated 2H-1-benzopyrans and 1,2-dihydronaphthalenes.The mercuration and subsequent carbonylation of o-R1OC6H4CCR2 1=Si(t-Bu)Me2, R2=CH3; R1=CH3, R2=o-C6H4OCH3> has provided a new approach to the coumarin and coumestan ring systems.
- Larock, Richard C.,Harrison, L. Wayne
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p. 4218 - 4227
(2007/10/02)
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- Alteration of relative affinities toward myocardial and vascular β adrenoceptors induced by side-chain substitution of aryloxypropanolamines1
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Several conformationally defined aryloxypropanolamines of the type ArOCH2CH(OH)CH(R)NHR1 have been synthesized and tested in vivo for β-adrenoceptor blockade. Key intermediates in the syntheses were the appropriate cis- and trans-disubstituted olefins. Epoxidation of the olefins, followed by amination of the resulting cis- and trans-epoxides, yielded the desired diastereomeric model compounds with a defined threo and erythro stereochemistry, respectively. All active compounds in this series exhibit a simple, bimolecular, competitive antagonism at β adrenoceptors. Proper substitutions of the alkanolamine side chain result in vascular selective or cardioselective β-adrenoceptor antagonists, probably as a consequence of the sterically altered ability to interact with β1 and β2 adrenoceptors. dl-erythro-1-Phenoxy-3-[3,4-dimethoxyphenethyl)amino] butan-2-ol is a cardioselective β-adrenoceptor antagonist with a selectivity ratio significantly higher than that of practolol (β1/β2>40 vs. β1/β2=22) but of equal potency (pA2 values = 6.66 and 6.64, respectively). Phenyl substitution at C-3 of the alkanolamine side chain drastically reduces affinity to both types of β adrenoceptors (pA25.0), thus representing a cutoff point. It is concluded that steric factors, as manifested by bulk tolerance at various parts of the aryloxypropanolamine side chain, are major determinants of affinity toward β-adrenoceptor subtypes. β-Adrenoceptor blockade is unrelated to the lipophilic character of the test compounds.
- Shtacher,Rubinstein,Somani
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p. 678 - 683
(2007/10/04)
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