195044-14-5Relevant articles and documents
Steric Protection of Rhodium-Nitridyl Radical Species
Rebreyend, Christophe,Mouarrawis, Valentinos,Siegler, Maxime A.,van der Vlugt, Jarl Ivar,de Bruin, Bas
, p. 4249 - 4255 (2019)
In an attempt to synthesize a mononuclear rhodium nitridyl complex with a reduced tendency to undergo nitridyl radical N–N coupling, we synthesized a bulky analog of Milstein's bipyridine-based PNNH ligand, bearing a tert-butyl group at the 6′ position of the bipyridine moiety. A three-step synthetic route toward this new bulky tBu3PNNH ligand was developed, involving a selective nucleophilic substitution step, followed by a Stille coupling and a final hydrophosphination step to afford the desired 6-(tert-butyl)-6′-[(di-tert-butylphosphino)methyl]-2,2′-bipyridine (tBu3PNNH) ligand. This newly developed tBu3PNNH ligand was incorporated in the synthesis of the sterically protected azide complex [Rh(N3)(tBu3PNNH)]. We explored N2 elimination form this species using photolysis and thermolysis, hoping to synthesize a mononuclear rhodium complex with a terminal nitrido moiety. Characterization of the reaction product(s) using NMR, coldspray HR-ESI-MS and EPR spectroscopy shows that the material is paramagnetic, and data obtained by MS spectrometry revealed masses corresponding with both monomeric and dimeric nitrido/nitridyl complexes. NMR only reveals broad uncharacteristic signals and the complex is EPR silent at 8K or above. The combined data point to formation of a paramagnetic [(tBu3PNN)Rh(μ-N)Rh(tBu3PNN)] species. It thus seems that despite its three tBu groups the new ligand is not bulky enough to prevent formation of Rh–N–Rh bridged species. However, the increased steric environment does prevent further reaction with carbon monoxide, which is unable to coordinate to rhodium.
Nickel, Ruthenium, and Rhodium NCN-Pincer Complexes Featuring a Six-Membered N-Heterocyclic Carbene Central Moiety and Pyridyl Pendant Arms
Jiang, Yanmin,Gendy, Chris,Roesler, Roland
, p. 1123 - 1132 (2018)
NCN pincer ligand precursor 1·HX (X = Cl, PF6), having a six-membered N-heterocyclic carbene central moiety and pyridyl pendant arms, was prepared via N-C cross-coupling of 2-bromo-6-tert-butylpyridine with propane-1,3-diamine, followed by ring closure with triethylorthoformate. The free ligand 1 was not accessible via deprotonation, yet its copper(I) complex 2 was prepared by reacting 1·HCl with CuI and potassium hexamethyldisilazide. It was used further as a transmetalation agent to prepare nickel(II) and ruthenium(II) dihalide NCN-pincer complexes 3a, 4a, and 4b, featuring a distorted square-pyramidal geometry at the metal, with the carbene ligand in the axial position. The rhodium(III) NCN-pincer complex 6b was obtained from 2 and [Rh(cod)Cl]2 via transmetalation followed by oxidation with Cu(I) in THF. The rhodium(III) NCC-pincer complex 9b was prepared under similar conditions in acetonitrile, where a spontaneous rollover cyclometalation occurred. Complex 9b has a distorted octahedral geometry, with the acetonitrile ligand trans to the carbene. Very short Ru-CNHC and Rh-CNHC bonds were measured in complexes 4a, 4b, and 9b. Halogen exchange was observed by 1H and 13C NMR spectroscopy in both ruthenium and rhodium systems during the transmetalation stage, and the purification was accomplished by pushing the respective equilibrium with excess halide.
MODULATORS OF CYSTIC FIBROSIS TRANSMEMBRANE CONDUCTANCE REGULATOR
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Paragraph 00391, (2021/02/19)
This disclosure provides modulators of Cystic Fibrosis Transmembrane Conductance Regulator (CFTR), pharmaceutical compositions containing at least one such modulator, methods of treatment of cystic fibrosis using such modulators and pharmaceutical compositions, and processes for making such modulators.
Chiral Memory in Silyl-Pyridinium and Quinolinium Cations
Fernandes, Anthony,Laye, Claire,Pramanik, Suman,Palmeira, Dayvson,Pekel, ?zgen ?mür,Massip, Stéphane,Schmidtmann, Marc,Müller, Thomas,Robert, Frédéric,Landais, Yannick
supporting information, p. 564 - 572 (2020/01/09)
Pyridine- and quinoline-stabilized silyl cations have been prepared, and their structure in condensed phases unambiguously assigned using 1H, 13C, 15N, 29Si, and 1H DOSY NMR as well as X-ray diffraction studies. Solid state structures thus show in both cases a stabilization of the cationic silicon center through an N-Si interaction and formation of a highly strained four-membered ring system. Chiral memory at the silicon atom in these heterocycle-stabilized silyl cations was also established, leading to various levels of selectivity depending on the nature of the heterocycle. Lowest energy conformations of the starting silanes obtained through DFT calculations, along with the isolation and characterization of the Si-centered chiral silyl cation intermediates, finally allowed to propose a plausible hypothesis as to the configurational stability of these silyl cations.
IRAK DEGRADERS AND USES THEREOF
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Paragraph 00920; 001832-001834, (2021/01/23)
The present invention provides compounds, compositions thereof, and methods of using the same. The compounds include an IRAK binding moiety capable of binding to IRAK4 and a degradation inducing moiety (DIM). The DIM could be DTM a ligase binding moiety (LBM) or lysine mimetic. The compounds could be useful as IRAK protein kinase inhibitors and applied to IRAK mediated disorders.
HETEROCYCLIC COMPOUNDS AND USES THEREOF
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Paragraph 0475-0477, (2019/04/25)
Heterocyclic compounds as Wee1 inhibitors are provided. The compounds may find use as therapeutic agents for the treatment of diseases and may find particular use in oncology.
N?-Acryloyllysine Piperazides as Irreversible Inhibitors of Transglutaminase 2: Synthesis, Structure-Activity Relationships, and Pharmacokinetic Profiling
Wodtke, Robert,Hauser, Christoph,Ruiz-Gómez, Gloria,J?ckel, Elisabeth,Bauer, David,Lohse, Martin,Wong, Alan,Pufe, Johanna,Ludwig, Friedrich-Alexander,Fischer, Steffen,Hauser, Sandra,Greif, Dieter,Pisabarro, M. Teresa,Pietzsch, Jens,Pietsch, Markus,L?ser, Reik
supporting information, p. 4528 - 4560 (2018/05/07)
Transglutaminase 2 (TGase 2)-catalyzed transamidation represents an important post-translational mechanism for protein modification with implications in physiological and pathophysiological conditions, including fibrotic and neoplastic processes. Consequently, this enzyme is considered a promising target for the diagnosis of and therapy for these diseases. In this study, we report on the synthesis and kinetic characterization of N?-acryloyllysine piperazides as irreversible inhibitors of TGase 2. Systematic structural modifications on 54 new compounds were performed with a major focus on fluorine-bearing substituents due to the potential of such compounds to serve as radiotracer candidates for positron emission tomography. The determined inhibitory activities ranged from 100 to 10?000 M-1 s-1, which resulted in comprehensive structure-activity relationships. Structure-activity correlations using various substituent parameters accompanied by covalent docking studies provide an advanced understanding of the molecular recognition for this inhibitor class within the active site of TGase 2. Selectivity profiling of selected compounds for other transglutaminases demonstrated an excellent selectivity toward transglutaminase 2. Furthermore, an initial pharmacokinetic profiling of selected inhibitors was performed, including the assessment of potential membrane permeability and liver microsomal stability.
NEAR-INFRARED-RAY-ABSORBING COMPOSITION, NEAR-INFRARED-RAY CUT FILTER USING SAME, MANUFACTURING METHOD THEREFOR, CAMERA MODULE, AND MANUFACTURING METHOD THEREFOR
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Paragraph 0813; 0814, (2017/01/02)
Provided are a near-infrared-ray-absorbing composition having strong near-infrared shielding properties when a cured film is produced, a near-infrared-ray cut filter, a manufacturing method therefor, a camera module, and a manufacturing method therefor. The near-infrared-ray-absorbing composition includes a copper complex obtained by reacting a compound (A) having at least two coordination sites with a copper component.
Allylation reactions of aldehydes with allylboronates in aqueous media: Unique reactivity and selectivity that are only observed in the presence of water
Kobayashi, Shu,Endo, Toshimitsu,Yoshino, Takumi,Schneider, Uwe,Ueno, Masaharu
supporting information, p. 2033 - 2045 (2013/09/23)
Zn(OH)2-catalyzed allylation reactions of aldehydes with allylboronates in aqueous media have been developed. In contrast to conventional allylboration reactions of aldehydes in organic solvents, the α-addition products were obtained exclusively. A catalytic cycle in which the allylzinc species was generated through a B-to-Zn exchange process is proposed and kinetic studies were performed. The key intermediate, an allylzinc species, was detected by HRMS (ESI) analysis and by online continuous MS (ESI) analysis. This analysis revealed that, in aqueous media, the allylzinc species competitively reacted with the aldehydes and water. An investigation of the reactivity and selectivity of the allylzinc species by using several typical allylboronates (6a, 6b, 6c, 6d) clarified several important roles of water in this allylation reaction. The allylation reactions of aldehydes with allylboronic acid 2,2-dimethyl-1,3-propanediol esters proceeded smoothly in the presence of catalytic amounts of Zn(OH)2 and achiral ligand 4d in aqueous media to afford the corresponding syn-adducts in high yields with high diastereoselectivities. In all cases, the α-addition products were obtained and a wide substrate scope was tolerated. Furthermore, this reaction was applied to asymmetric catalysis by using chiral ligand 9. Based on the X-ray structure of the Zn-9 complex, several nonsymmetrical chiral ligands were also found to be effective. This reaction was further applied to catalytic asymmetric alkylallylation, chloroallylation, and alkoxyallylation processes and the synthetic utility of these reactions has been demonstrated. Still waters run deep: The Zn(OH)2-catalyzed allylation of aldehydes with allylboronates in aqueous media exclusively afford the α-addition products. This reaction was also applied to alkylallylation, chloroallylation, and alkoxyallylation reactions. The role of water is discussed. Copyright
Biarylphosphonite gold(I) complexes as superior catalysts for oxidative cyclization of propynyl arenes into indan-2-ones
Henrion, Guilhem,Chavas, Thomas E. J.,Le Goff, Xavier,Gagosz, Fabien
supporting information, p. 6277 - 6282 (2013/07/11)
Striking gold: A series of variously functionalized propynyl arenes was smoothly converted into indan-2-ones by a new gold(I)-catalyzed oxidative cyclization process. [LAu]NTf2 (Tf=trifluoromethanesulfonyl) is a superior catalyst both in terms of yield and kinetics for the present transformation. Copyright
