93-54-9Relevant articles and documents
A new heterometallic coordination polymer: Synthesis, structure, and catalytic property
Liu, Qi-Feng,Liu, Wei,Cao, Yi-Po,Dong, Yan-Li,Liu, Hui-Min
, p. 153 - 157 (2017)
A new heterometallic-organic framework, namely [CuCa(tdc)2(DMF)]n(1 H2tdc = 2,5-thiophenedicarboxylic acid, DMF = N,N’-dimethylformamide), has been successfully obtained through the solvothermal reactions of CuCl2, Ca(NO3)2, and H2tdc. Single-crystal structural analysis reveals that compound 1 features a 3D framework with the irl topology. Compound 1 has potential unsaturated metal sites after the removal of the coordinated DMF molecules, so it exhibits excellent catalytic activity for the diethylzinc addition to benzaldehyde.
Kinetic investigations of product inhibition in the amino alcohol-catalyzed asymmetric alkylation of benzaldehyde with diethylzinc
Rosner, Thorsten,Sears, Patrick J.,Nugent, William A.,Blackmond, Donna G.
, p. 2511 - 2513 (2000)
(equation presented) In situ reaction rate measurements help to define the role of product inhibition in the asymmetric alkylation of benzaldehyde with diethylzinc using (-)-MIB as a chiral reagent. Reaction calorimetry and kinetic modeling demonstrated that the rate behavior over consecutive reactions may only be rationalized when reversible binding of the product alkoxide is taken into consideration. These results may have implications for the conversion dependence of product enantioselctivity in reactions using enantioimpure catalysts.
RZnI vs. R2Zn in Pd(0)-catalyzed cross-coupling reactions with thioimidates
Roberts, William P.,Ghosh, Indranath,Jacobi, Peter A.
, p. 279 - 284 (2004)
Thioimidates 1-Z undergo facile cross-coupling with Pd(0)-RZnI but are inert to Pd(0)-R2Zn. This difference is due to the lower Lewis acidity of R2Zn, as opposed to lower nucleophilicity. Various sources of RZnI (R = Me, Et) and Pd(0) were evaluated for their convenience and reactivity.
A novel approach to conformationally strained 2,2′-bipyridine thiacrown ethers and their chiral sulfoxides by sequential homo-coupling/DA-rDA reaction of 5,5′-bi-1,2,4-triazine-containing thiamacrocycles
?awecka, Justyna,Karczmarzyk, Zbigniew,Wolińska, Ewa,Olender, Ewa,Branowska, Danuta,Rykowski, Andrzej
, p. 3098 - 3104 (2011)
The synthesis of conformationally strained 2,2′-bipyridine thiamacrocycles 5, 6, 9, 10 and their chiral sulfoxides 11-14 is elaborated using, (1) homo-coupling of 1,2,4-triazine sulfide 3 with potassium cyanide and (2) Diels-Alder/retro Diels-Alder (DA-rDA) with 2,5-norbornadiene or 1-pyrrolidino-1-cyclopentene as the key steps. The crystal structure determinations of 4-6 and the theoretical calculations at DFT/B3LYP/6-311 G level were conducted thus establishing conformational preferences of the target thiamacrocycles
Hydrolysis of Phosphonothioates with a Binaphthyl Group: P-Stereogenic O-Binaphthyl Phosphonothioic Acids and Their Use as Optically Active Ligands and Chiral Discriminating Agents
Kuwabara, Kazuma,Maekawa, Yuuki,Minoura, Mao,Murai, Toshiaki
, p. 1375 - 1379 (2018)
The hydrolysis of phosphonothioates with a binaphthyl group afforded the first example of O-(2′-hydroxy)binaphthyl phosphonothioic acids in good to high yields and >95:5 diastereoselectivity. The reaction proceeds via an axis-to-center chirality-transfer reaction. The ability of these acids to act as chiral molecular auxiliaries was demonstrated by using them as optically active ligands for the asymmetric ethylation of benzaldehyde and as a chiral discriminating agent for chiral aliphatic amines.
Catalytic enantioselective addition of diethylzinc to 1,3-dithian-2-yl substituted aliphatic aldehydes: A new approach to optically active 2-(hydroxyalkyl)-1,3-dithianes
Wilken, Joerg,Winter, Martin,Stahl, Ingfried,Martens, Juergen
, p. 1067 - 1071 (2000)
Asymmetric synthesis of 2-(hydroxyalkyl)-1,3-dithianes was achieved in good yields of up to 81% by using various 1,3-dithian-2-yl-substituted aliphatic aldehydes as substrates in the catalytic enantioselective addition of diethylzinc. With fair enantiomeric ratios of up to 85:15 in the enantiocontrolled ethylation step this synthetic approach provides an entry towards potential chiral building blocks. Copyright (C) 2000 Elsevier Science Ltd.
Best design of heterogenized β-aminoalcohols for improvement of enantioselective addition of diethylzinc to benzaldehyde
Abramson,Lasperas,Galarneau,Desplantier-Giscard,Brunel
, p. 1773 - 1774 (2000)
Covalent immobilization of (1R,2S)-(-)-ephedrine, used as a model molecule of β-aminoalcohols, on the surface of MCM-41-type mesoporous aluminosilicates, performed by a new sol-gel method, leads to chiral auxiliaries which show greatly enhanced rates and ee's compared to those reported up to now in the enantioselective addition of diethylzinc to benzaldehyde.
Chemoselective Hydrogenation of Olefins Using a Nanostructured Nickel Catalyst
Klarner, Mara,Bieger, Sandra,Drechsler, Markus,Kempe, Rhett
supporting information, p. 2157 - 2161 (2021/05/21)
The selective hydrogenation of functionalized olefins is of great importance in the chemical and pharmaceutical industry. Here, we report on a nanostructured nickel catalyst that enables the selective hydrogenation of purely aliphatic and functionalized olefins under mild conditions. The earth-abundant metal catalyst allows the selective hydrogenation of sterically protected olefins and further tolerates functional groups such as carbonyls, esters, ethers and nitriles. The characterization of our catalyst revealed the formation of surface oxidized metallic nickel nanoparticles stabilized by a N-doped carbon layer on the active carbon support.
Reduction of carbonyl compounds via hydrosilylation catalyzed by well-defined PNP-Mn(I) hydride complexes
Weber, Stefan,Iebed, Dina,Glatz, Mathias,Kirchner, Karl
, p. 635 - 639 (2021/06/17)
Reduction reactions of unsaturated compounds are fundamental transformations in synthetic chemistry. In this context, the reduction of polarized double bonds such as carbonyl or C=C motifs can be achieved by hydrogenation reactions. We describe here a highly chemoselective Mn(I)-based PNP pincer catalyst for the hydrosilylation of aldehydes and ketones employing polymethylhydrosiloxane (PMHS) as inexpensive hydrogen donor. Graphic abstract: [Figure not available: see fulltext.]