139163-56-7Relevant articles and documents
The versatile, efficient, and stereoselective self-assembly of transition-metal helicates by using hydrogen-bonds
Telfer, Shane G.,Kuroda, Reiko
, p. 57 - 68 (2005)
A diverse range of dinuclear double-stranded helicates in which the ligand strand is built up by using hydrogen-bonding has been synthesized. The helicates, formulated as [Co2(L)2(L-H)2X 2], readily self-assemble from a mixture of a suitable pyridine-alcohol compound (L; for example, 6-methylpyridine-2-melhanol, 1), and a CoX2 salt in the presence of base. Nine such helicates have been characterized by X-ray crystallography. For helicates derived from the same pyridine-alcohol precursor, a remarkable regularity was found for both the molecular structure and the crystal packing arrangements, regardless of the nature of the ancillary ligand (X). A notable exception was observed in the solid-state structure of [Co2(1)2(1-H)2(NCS) 2] for which intermolecular nonbonded contacts between the sulfur atoms (S...S = 3.21 A) lead to the formation of 1D chains. Helicates derived from (R)-6-methylpyridine-2-methanol (2) are soluble in solvents such as CH3CN and CH2Cl2, and their self-assembly could be monitored in solution by 1H NMR, UV/Vis, and CD titrations. No intermediate complexes were observed to form in a significant concentration at any point throughout these titrations. The global thermodynamic stability constant of [Co2(2)2-(2-H)2(NO 3)2] was calculated from spectrophotometric data to be logβ = 8.9(8). The stereoisomerism of these helicates was studied in some detail and the self-assembly process was found to be highly stereoselective. The chirality of the ligand precursors can control the absolute configuration of the metal centers and thus the overall helicity of the dinuclear assemblies. Furthermore, the enantiomers of rac-6-methylpyridine-2-methanol (3) undergo a self-recognition process to form exclusively bomochiral helicates in which the four pyridine-alcohol units possess the same chirality.
NEW MACROCYCLIC LRRK2 KINASE INHIBITORS
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Page/Page column 249-250, (2021/11/13)
Compounds of formula (I): wherein R, X1, X2, X3, Z1, Z2, Z3, A and Ra are as defined in the description. Medicaments.
Copper-catalyzed asymmetric reductions of aryl/heteroaryl ketones under mild aqueous micellar conditions
Etemadi-Davan, Elham,Fialho, David M.,Gadakh, Amol,Langner, Olivia C.,Lipshutz, Bruce H.,Sambasivam, Ganesh,Takale, Balaram S.
supporting information, p. 3282 - 3286 (2021/05/29)
Enantioselective syntheses of nonracemic secondary alcohols have been achieved in an aqueous micellar medium via copper-catalyzed (Cu(OAc)2·H2O/(R)-3,4,5-MeO-MeO-BIPHEP) reduction of aryl/heteroaryl ketones. This methodology serves as a green protocol to access enantio-enriched alcohols under mild conditions (0-22 °C) using a base metal catalyst, together with an inexpensive, innocuous, and convenient stoichiometric hydride source (PMHS). The secondary alcohol products are formed in good to excellent yields with ee values greater than 90%.
Palladium-Catalyzed Selective Reduction of Carbonyl Compounds
Sarkar, Nabin,Mahato, Mamata,Nembenna, Sharanappa
, p. 2295 - 2301 (2020/05/18)
Two new examples of structurally characterized β-diketiminate analogues i.e., conjugated bis-guanidinate (CBG) supported palladium(II) complexes, [LPdX]2; [L= {(ArHN)(ArN)–C=N–C=(NAr)(NHAr)}; Ar = 2,6-Et2-C6H3], X = Cl (1), Br (2) have been reported. The synthesis of complexes 1–2 was achieved by two methods. Method A involves deprotonation of LH by nBuLi followed by the treatment of LLi (insitu formed) with PdCl2 in THF, which afforded compound 1 in good yield (75 %). In Method B, the reaction between free LH and PdX2 (X = Cl or Br) in THF allowed the formation of complexes 1 (Yield 73 %) and 2 (Yield 52 %), respectively. Moreover, these complexes were characterized thoroughly by several spectroscopic techniques (1H, 13C NMR, UV/Vis, FT-IR, and HRMS), including single-crystal X-ray structural and elemental analyses. In addition, we tested the catalytic activity of these complexes 1–2 for the hydroboration of carbonyl compounds with pinacolborane (HBpin). We observed that compound 1 exhibits superior catalytic activity when compared to 2. Compound 1 efficiently catalyzes various aldehydes and ketones under solvent-free conditions. Furthermore, both inter- and intramolecular chemoselectivity hydroboration of aldehydes over other functionalities have been established.
Multifaceted chelating μ-(η3:η3-antifacial)-(cis-C4R2H2) coordination motif in binuclear complexes
Liu, Cham-Chuen,Chan, Michael C. W.,Lo, Po-Kam,Lau, Kai-Chung,Yiu, Shek-Man
supporting information, p. 11056 - 11059 (2016/09/19)
A novel μ-C4R2H2 core structure (formed by an unprecedented regioselective, redox-neutral C(sp2)-C(sp2) coupling process) in binuclear group 4 complexes displays adaptable coordination and accommodates different metal sizes, and is sufficiently robust to promote interesting catalytic reactivity at the bimetallic centers.
Chiral pincer ruthenium and osmium complexes for the fast and efficient hydrogen transfer reduction of ketones
Baratta, Walter,Benedetti, Fabio,Del Zotto, Alessandro,Fanfoni, Lidia,Felluga, Fulvia,Magnolia, Santo,Putignano, Elisabetta,Rigo, Pierluigi
experimental part, p. 3563 - 3570 (2010/10/03)
A series of chiral HCNN ligands ((S)-1b-g) (S)-2-(1-aminoethyl)-6-(aryl) pyridine (aryl = 4-MeO-phenyl, 1b; 4-CF3-phenyl, 1c; 3,5-di-Me-phenyl, 1d; 3,5-di-CF3-phenyl, 1e; 1-naphthyl, 1f; 2-naphthyl, 1g) were synthesized starting from commercial 2-acetyl-6- bromopyridine (2), by a chemoenzymatic method involving the dynamic kinetic resolution of the corresponding secondary alcohol (rac-3). The conversion of the resulting (R)-3, obtained in 98% ee, into the homochiral amine ((S)-6), followed by Suzuki coupling with the appropriate arylboronic acids 7b-g, gave access to (S)-1b-g, isolated in 97% ee, with an overall yield up to 50%. The in situ generated pincer complexes [MCl(CNN)(PP)] (M = Ru, Os; PP = Josiphos diphosphine), prepared from [MCl2(PPh3)3], (R,S)-Josiphos diphosphines, and the ligands (S)-1b-g, were found to efficiently catalyze the asymmetric transfer hydrogenation of acetophenone in 2-propanol at 60 °C and in the presence of NaOiPr. On the basis of these data, the 2-naphthyl ruthenium and osmium derivatives [RuCl(CNN)((R,S)-Josiphos*] (8) (HCNN = (S)-1g) and [OsCl(CNN)(PP)] (PP = (R,S)-Josiphos, 9, and (R,S)-Josiphos*, 10) were isolated from [MCl2(PPh 3)3], (R,S)-Josiphos diphosphines, and the ligand (S)-1g. Complexes 8 and 10, displaying the correctly matched chiral PP and CNN - ligands, are highly active and productive catalysts for the transfer hydrogenation of alkyl aryl ketones and methyl pyridyl ketones with TOF = 105-106 h-1, using 0.005 mol % of catalysts and achieving up to 99% ee. The comparison of the catalytic activity of these pincer complexes shows that Ru and Os derivatives display similar rate and enantioselectivity.
Branch-selective reductive coupling of 2-vinyl pyridines and imines via rhodium catalyzed C-C bond forming hydrogenation
Komanduri, Venukrishnan,Grant, Christopher D.,Krische, Michael J.
supporting information; experimental part, p. 12592 - 12593 (2009/05/08)
Hydrogenation of 2-vinyl azines 1a-1e in the presence of N-arylsulfonyl imines 2a-2l at ambient temperature and pressure employing cationic rhodium catalysts ligated by tri-2-furylphosphine results in regioselective reductive coupling to furnish branched
INHIBITORS OF JANUS KINASES
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Page/Page column 112, (2009/01/23)
The instant invention provides for compounds that inhibit the four known mammalian JAK kinases (JAK1, JAK2, JAK3 and TYK2) and PDK1. The invention also provides for compositions comprising such inhibitory compounds and methods of inhibiting the activity of JAK1, JAK2, JAK3 TYK2 and PDK1 by administering the compound to a patient in need of treatment for myeloproliferative disorders or cancer.
Dihydropyrazolopyrimidinone derivatives
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Page/Page column 57, (2008/06/13)
The invention relates to compounds of a general formula (I): wherein Ar1 is an optionally-substituted aryl or heteroaromatic group; R1 is an optionally-substituted lower alkyl, lower alkenyl, lower alkynyl or cyclo-lower alkyl group, or is an aryl, aralkyl or heteroaromatic group optionally having a substituent; R2 is a hydrogen atom, a lower alkyl group, a lower alkenyl group or a lower alkynyl group, or is an aryl, aralkyl or heteroaromatic group optionally having a substituent; R3 is a hydrogen atom or a lower alkyl group; R4 is a hydrogen atom, a halogen atom, a hydroxyl group, a lower alkyl group or a group of —N(R1k)R1m; T and U are a nitrogen atom or a methine group, etc. The compounds of the invention have excellent Weel kinase-inhibitory effect and are therefore useful in the field of medicines, especially treatment of various cancers.
Chiral Pyridines: Optical Resolution of 1-(2-Pyridyl)- and 1-[6-(2,2′-Bipyridyl)]ethanols by Lipase-Catalyzed Enantioselective Acetylation
Uenishi, Jun'ichi,Hiraoka, Takao,Hata, Shinichiro,Nishiwaki, Kenji,Yonemitsu, Osamu,Nakamura, Kaoru,Tsukube, Hiroshi
, p. 2481 - 2487 (2007/10/03)
The resolution of racemic 1-(2-pyridyl)ethanols 2a-n, including the 2,2′-bipyridyl and isoquinolyl derivatives, by lipase-catalyzed asymmetric acetylation with vinyl acetate is reported. The reactions were carried out in diisopropyl ether at either room temperature or 60°C using Candida antarctica lipase (CAL) to give (R)-acetate and unreacted (S)-alcohol with excellent enantiomeric purities in good yields. The reaction rate was relatively slow at room temperature for substrates bearing an sp3-type carbon at the 6-position on the pyridine ring, such as 2c, 2d, and 2e, and for those bearing 1-hydroxypropyl and allyl groups at the 2-position on the pyridine ring, such as 21 and 2m. In such cases, a higher temperature was required. Thus, when the reaction was conducted at 60°C, it was accelerated 3- to 7-fold without losing the high enantiospecificity. However, the reaction of homoallylic alcohol 2n was not complete, even when the reaction was continued for a longer period of time at 60°C. This enzymatic resolution can be used practically in a wide range of reaction scales from 10 mg to 10 g or more. This catalyst can be used repeatedly with a 5-10% loss of the initial activity with each use.
