Xi,Xn:;113439-83-1Relevant articles and documents
Autotandem Catalysis: Inexpensive and Green Access to Functionalized Ketones by Intermolecular Iron-Catalyzed Amidoalkynylation/Hydration Cascade Reaction via N-Acyliminium Ion Chemistry
Abdallahi, Sidi Mohamed,Ewies, Ewies F.,El-Shazly, Mohamed,Ould Elemine, Brahim,Hadou, Abderrahmane,Moncol, Ján,Lawson, Ata Martin,Daich, Adam,Othman, Mohamed
supporting information, p. 15440 - 15449 (2021/10/07)
Iron-based catalysts were applied in cascade-type reactions for the synthesis of different carbonyl compounds. The reactions proceeded by a new iron-catalyzed cascade of alkynylation/hydration by using both the σ- and π-Lewis acid properties of iron salts. The alkynylation reactions of several endo and exocyclic acetoxylactams were achieved with three different catalysts including FeCl3 ? 6H2O, FeCl3, and Fe(OTf)3 showing the efficiency of σ-Lewis acidity of iron (III) salts in catalyzing the alkynylation reaction. We also demonstrated that the reaction sequence could be shortened by the direct use of hydroxylactams, leading to an environmentally friendly protocol, avoiding the need to perform unnecessary lengthy steps. A combination of the hard/soft iron Lewis acid properties was then used to implement an unprecedented tandem intermolecular alkynylation/intramolecular hydration sequence allowing expedient access to a new carbonyl structures from trivial materials.
Gold-Catalyzed Regioselective Oxyfluorination/Oxydifluorination vs. Diketonization of Phthalimido-Protected Propargylamines with Selectfluor
Arcadi, Antonio,Marsicano, Vincenzo,Michelet, Véronique
supporting information, (2022/01/22)
Alkyl- and aryl-substituted N-propargyl phthalimides were used as valuable building blocks for the selective formation of the corresponding α-fluoro, β-phthalimido ketones, α,α-difluoro, β-phthalimido ketones or β-phthalimido α-diketones by means of gold-catalyzed oxyfluorination/oxydifluorination or dioxygenation reactions. The key factors addressing the product selectivity control were determined. The simultaneous assembly of the quinoxaline nucleus and the removal of the phthalimido-protecting group were tested. Reaction mechanisms of the different reaction pathways are assumed.
Experimental and computational evidence on gold-catalyzed regioselective hydration of phthalimido-protected propargylamines: An entry to β-amino ketones
Arcadi, Antonio,Aschi, Massimiliano,Marsicano, Vincenzo,Michelet, Véronique
supporting information, p. 9438 - 9447 (2020/12/15)
The results of our investigations on the Au-catalyzed regioselective hydration reaction of both alkyl- A nd aryl-substituted N-propargyl phthalimides directed to the selective formation of the corresponding β-phthalimido ketones are described. Experimental data, in particular the observed regioselectivity, have been qualitatively supported by quantum-chemical calculations carried out on model systems in the framework of Density Functional Theory (DFT) followed by quantum theory of atoms in molecules (QTAIMS). Our results suggest that the electronic features of the initial adduct between the propargyl triple bond and the Au(i) catalyst, in particular the character of the gold-triple bond interaction, are essential for the observed regioselectivity. Other effects, such as the presence of the solvent and the formation of a H-bond between the water molecule and the phthalimido moiety, although apparently irrelevant for the regioselectivity, have proven to be kinetically and catalytically rather important. This journal is
8 - SULFO - IMIDAZOTETRAZIN- 4 - ONE COMPOUNDS AND THEIR USE AS ANTICANCER DRUG
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Page/Page column 87, (2012/07/13)
Compounds of formula (I) and pharmaceutically acceptable salts, hydrates or solvates thereof are provided (I) wherein B, X, and Y are as defined herein. The compounds are of use in methods of regulating cell proliferation, inhibiting cell cycle progressio
Tungsten(0)- and rhenium(I)-catalyzed tandem cyclization of acetylenic dienol silyl ethers based on geminal carbo-functionalization of alkynes
Kusama, Hiroyuki,Karibe, Yusuke,Imai, Rie,Onizawa, Yuji,Yamabe, Hokuto,Iwasawa, Nobuharu
supporting information; experimental part, p. 4839 - 4848 (2011/06/21)
Tungsten(0)- and rhenium(I)-catalyzed reactions of acetylenic dienol silyl ethers based on the concept of geminal carbo-functionalization of alkynes are reported. Treatment of 3-siloxy-1,3-diene-7-ynes with catalytic amounts of [W(CO)6] or [ReCl(CO)5] under photoirradiation conditions gives synthetically useful bicyclo[3.3.0]octane derivatives in good yields. Extremely high catalytic activity is noted for the rhenium(I) complex. The reaction has been extended to substrates containing a nitrogen atom in their tethers. In this case, two kinds of synthetically useful heterocyclic compounds-the 2-azabicyclo[3.3.0]octane derivatives 9 and the monocyclic dihydropyrroles 10, with allenyl substituents-are obtained, and selective preparation of either product can be achieved through the use of an appropriate combination of the nitrogen substituent and the type of the rhenium(I) catalyst. The 2-azabicyclo[3.3.0]octane derivatives 9 are obtained selectively by carrying out treatment of N-Ns derivatives in the presence of [ReCl(CO) 4(PPh3)], whereas the dihydropyrrole derivatives 10 are obtained by treatment of N-Mbs derivatives with [ReCl(CO)5]/ AgSbF6. Finally, we have applied this geminal carbo-functionalization to one-carbon-elongated substrates containing N-Ts moieties in their tethers. Selective 5-exo cyclization is achieved in the presence of gold(I) or rhenium(I) catalysts, whereas 6-endo cyclization is observed on use of [W(CO) 6]. Geminal carbo-functionalization of 3-siloxy-1,3-dien-7-ynes leading to bicyclo[3.3.0]octane derivatives is achieved through electrophilic activation of alkynes by tungsten(0) and rhenium(I) catalysts (see graphic). Extremely high activity is noted for rhenium(I) catalysts. Furthermore, selective preparation of two different classes of heterocyclic compounds from 5-aza-3-siloxy-1,3-dien-7-ynes is also achieved by appropriate choice of the rhenium(I) catalyst and the protecting group on the nitrogen. Copyright
Discovery of orally available spirodiketopiperazine-based CCR5 antagonists
Nishizawa, Rena,Nishiyama, Toshihiko,Hisaichi, Katsuya,Hirai, Keisuke,Habashita, Hiromu,Takaoka, Yoshikazu,Tada, Hideaki,Sagawa, Kenji,Shibayama, Shiro,Maeda, Kenji,Mitsuya, Hiroaki,Nakai, Hisao,Fukushima, Daikichi,Toda, Masaaki
experimental part, p. 5208 - 5223 (2010/09/18)
Using the previously reported novel spirodiketopiperazine scaffold, the design and synthesis of orally available CCR5 antagonists was undertaken. Compounds possessing a carboxylic acid function in the appropriate position showed improved oral exposure (AU
The Stereochemistry of Organometallic Compounds. XXXII. Hydrocyanation of Derivatives of Amino Alkynes
Jackson, W. Roy,Perlmutter, Patrick,Smallridge, Andrew J.
, p. 1201 - 1208 (2007/10/02)
The hydrocyanation of a range of amino alkyne derivatives has been studied by using nickel-based catalyst systems.The phthalimido derivatives have been shown to give good yields of unsaturated cyano amine derivatives, and some of these have been converted into both saturated and unsaturated amino acids.
THE HYDROCYANATION ROUTE TO β- AND γ-AMINO ACIDS. A SYNTHESIS OF α-METHYLENE-β-ALANINE
Jackson, W. Roy,Perlmutter, Patrick,Smallridge, Andrew
, p. 1983 - 1984 (2007/10/02)
Hydrocyanation of several phthalimidoalkynes proceeds with good regioselection yielding products which were easily converted into unsaturated β- and γ-amino acids.
Electron Delocalisation and Stabilisation in Substituted Amino- and Hydroxypropynyl Radicals
MacInnes, Iain,Walton, John C.
, p. 1077 - 1082 (2007/10/02)
A series of aminopropynes, RCCCH2NH2 (R = H, Me, t-Bu, Me3Si), RCCCH2N(SiMe3)2, and hydroxypropynes RCCCH2OH (R = H, Me, t-Bu, Me3Si, CF3, and EtO2C), were prepared and the corresponding α-aminopropynyl and α-hydroxypropynyl radicals were examined by e.s.r. spectroscopy.For the first series, the C-N bond rotation barriers were determined from the exchange broadening in the spectra and hence radical stabilization energies were estimated.The spin distribution in these series indicated an extra delocalisation in radicals with captodative substitution.
