74137-36-3Relevant academic research and scientific papers
Synthesis and reactivities of new NCN-type pincer complexes of nickel
Cloutier, Jean-Philippe,Vabre, Boris,Moungang-Soum, Berline,Zargarian, Davit
, p. 133 - 145 (2015)
This report describes the preparation, characterization, and reactivities of a new family of Ni(II) complexes based on the pincer-type ligands R-NCNpz (κN,κC,κN-1,3-bis(pyrazole),5-R-C6H2; R = H, OMe). Ullman coupling of pyrazole with 1,3-diiodobenzene or 1,3-dibromo-5-methoxybenzene gave the compounds R-NC(H)Npz, which were refluxed in xylene with (i-PrCN)NiBr2 and NEt3 to give the complexes (NCNpz)NiBr (1) and (MeO-NCNpz)NiBr (2) via C-H nickelation. The aryloxide derivative (NCNpz)Ni(OAr) (3; Ar = 2,6-t-Bu2-4-Me-OC6H2) was prepared by treating the bromo precursor 1 with NaOAr, whereas the analogous reaction with NaOEt gave instead the protonated or ethoxy-functionalized ligand NC(H)Npz (major) and NC(OEt)Npz (minor). The new complexes 1-3 were fully characterized, including solid-state structures. Attempted oxidation of these complexes failed to give the target trivalent derivatives, leading instead to intractable, deeply colored Ni-containing solids, various ligand-derived side products, or an unusual I2 adduct. For example, treatment of 1 or 2 with N-bromosuccinimide gave sparingly soluble dark solids that appear to be paramagnetic, whereas 3 reacted with Br2 to give short-lived dark intermediates that decomposed over seconds to give ArOH. Reaction of the bromo complexes with aqueous H2O2 (30%) gave the functionalized ligands Br-NC(OH)Npz and NC(OH)Npz (from 1) or MeO-NC(OH)Npz (from 2), whereas 1 reacted with I2 to generate (NCNpz)NiBr·I2, an iodine adduct displaying weak Br-I interactions. Heating 1 in EtOH in air generated NC(OEt)Npz. This ligand derivatization could be extended to other alcohols (MeOH, i-PrOH, CF3CH2OH) and amines (morpholine, cyclohexylamine, aniline). Possible mechanistic scenarios for the observed oxidative, Ni-promoted Cipso-X bond formation reactions are discussed in the context of relevant literature precedents.
Catalytic Formation of Coordination-Based Self-Assemblies by Halide Impurities
Bobylev, Eduard. O.,De Bruin, Bas,Reek, Joost N. H.
, p. 12498 - 12505 (2021)
The dynamics of metal organic polyhedra (MOP) play a crucial role for their application in catalysis and host-guest chemistry and as functional materials. In this contribution, we study the influence of possible contaminations of different metal precursors on the kinetic properties of MOP. Exemplary five different MOP are studied with metal precursors of varying quality. The metal precursors are either obtained from commercial sources or prepared by various literature procedures. Studies into the self-assembly process using 1H NMR and MS analyses were performed on Pt2L4, Pd2L4, Pd6L12, Pd12L24, and Ni4L6 assemblies. Commonly found impurities are shown to play a prominent role guiding selective formation of MOP, as they allow for an escape from otherwise kinetically trapped intermediates. The energy requirement for selective sphere formation is significantly lowered in many examples providing evidence for a catalytic role of halide impurities/additives in the self-assembly process. Furthermore, even though most analytical features such as 1H NMR and MS analyses show identical results for assemblies with different types of metal precursors, the dynamics of formed assemblies differs significantly if slightly less pure starting materials are used. Tiny amounts of halide contaminations make the MOP more dynamic, which can play an important role for substrate diffusion especially if bulky substrates are used. We believe that this study on the influence of impurities (which were shown to be present in some commercial sources) on the kinetic properties of MOP together with procedures of obtaining high purity metal precursors provides important information for future material preparation and provides a better understanding of already known examples.
Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
supporting information, p. 3723 - 3728 (2021/04/07)
We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
Amphipathic rhombic supramolecular metal macrocycle as well as preparation method and application thereof (by machine translation)
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Paragraph 0052-0054; 0061-0062, (2021/01/11)
The invention discloses an amphipathic rhombic supramolecular metal macrocyclic compound as well as a preparation method and application thereof. The structure of the amphipathic rhombic supramolecular metal macrocyclic compound is shown as a formula (I). The preparation method of the amphipathic rhombic supramolecular metal macrocyclic compound comprises the following steps: mixing a glucose group-modified 120°-bipyridine ligand L and a methoxy functionalized 60°-diplatinum receptor A and the like, and forming an amphipathic rhombic supramolecular metal macrocyclic compound by self-assembly of the orientation coordinate bonds between the two Pt (II)- N. The invention further provides a preparation of the amphipathic rhombic supramolecular metal macrocyclic compound Use of a vector. (by machine translation)
A containing pyrimidine group rigid conjugated macrocyclic compound and its preparation method and application (by machine translation)
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Paragraph 0034; 0046; 0047, (2017/05/18)
The invention relates to a containing pyrimidine group rigid conjugated macrocyclic compound and its preparation method and application, structure of the compound of the general formula: wherein n=1, 2, 3, 4, 5. The preparation comprises: to the rigid part of the 3, 5 - dibromide fluoride as the raw material for the synthesis of 3, 5 - di bromo methyl ether, then tribromide the boron escapes methylation reaction for the synthesis of 3, 5 - two-bromophenol, the linear part of the 3 - chloro - 2 - chloromethyl propylene as the starting material, to obtain the linear part of the intermediate, after 3, 5 - b bromophenol under alkaline conditions with the linear part of the intermediate synthesis of 3, 5 - b bromophenylacetic long chain ether, using 3, 5 - b bromophenylacetic long chain ethergathers two boron mellowly with dual-frequency which Miyaura reaction on synthetic monomer II; monomer II with 5 - bromo - 2 through the Suzuki coupling reaction of iodine pyrimidine synthetic monomer III; the use of monomer II and monomer III Suzuki coupling to get through. The invention the resulting compounds as functional material application. (by machine translation)
Charge-transfer-featured materials - Promising hosts for fabrication of efficient OLEDs through triplet harvesting via triplet fusion
Zhou, Jie,Chen, Ping,Wang, Xu,Wang, Yan,Wang, Yi,Li, Feng,Yang, Minghui,Huang, Yan,Yu, Junsheng,Lu, Zhiyun
supporting information, p. 7586 - 7589 (2014/07/08)
A charge-transfer-featured naphthalimide derivative with a small exchange energy but a lower lying 3ππ* state than 3CT state is found to contribute to triplet harvesting through a P-type rather than an E-type delayed fluorescence, and could act as a quite promising host to achieve highly efficient OLEDs.
Thiophene-coated functionalized M12L24 spheres: Synthesis, characterization, and electrochemical properties
Jiang, Fei,Wang, Ning,Du, Zhengkun,Wang, Jun,Lan, Zhenggang,Yang, Renqiang
supporting information, p. 2230 - 2234,5 (2020/08/24)
Instant balls: Well-defined thiophene-coated functional nanospheres were synthesized by instantaneous self-assembly of twelve 90° Pd II-containing compounds and twenty-four 120° organic bidentate ligands in acetone. This solvent system was efficient to prepare the self-assembled complexes, facilitating isolation and purification. The self-assembled functional nanospheres exhibited interesting electrochemical properties. Copyright
Synthesis and pharmacological evaluation of N -(3-(1 H -Indol-4-yl)-5-(2- methoxyisonicotinoyl)phenyl)methanesulfonamide (LP-261), a potent antimitotic agent
Shetty, Rupa S.,Lee, Younghee,Liu, Bin,Husain, Arifa,Joseph, Rhoda W.,Lu, Yixin,Nelson, David,Mihelcic, John,Chao, Wenchun,Moffett, Kristofer K.,Schumacher, Andreas,Flubacher, Dietmar,Stojanovic, Aleksandar,Bukhtiyarova, Marina,Williams, Ken,Lee, Kyoung-Jin,Ochman, Alexander R.,Saporito, Michael S.,Moore, William R.,Flynn, Gary A.,Dorsey, Bruce D.,Springman, Eric B.,Fujimoto, Ted,Kelly, Martha J.
experimental part, p. 179 - 200 (2011/03/19)
The synthesis and optimization of a series of orally bioavailable 1-(1H-indol-4-yl)-3,5-disubstituted benzene analogues as antimitotic agents are described. A functionalized dibromobenzene intermediate was used as a key scaffold, which when modified by sequential Suzuki coupling and Buchwald-Hartwig amination provided a flexible entry to 1,3,5-trisubstituted phenyl compounds. A 1H-indol-4-yl moiety at the 1-position was determined to be a critical feature for optimal potency. The compounds have been shown to induce cell cycle arrest at the G2/M phase and demonstrate efficacy in both cell viability and cell proliferation assays. The primary site of action for these agents is revealed by their colchicine competitive inhibition of tubulin polymerization, and a computational model has been developed for the association of these compounds to tubulin. An optimized lead LP-261 significantly inhibits growth of a human non-small-cell lung tumor (NCI-H522) in a mouse xenograft model.
Synthesis of the tetracyclic core of tetrapetalone a enabled by a pyrrole reductive alkyation
Marcus, Andrew P.,Sarpong, Richmond
supporting information; experimental part, p. 4560 - 4563 (2010/12/25)
The tetracyclic framework of the tetrapetalone A aglycon has been secured through synthesis. A reductive pyrrole alkylation enables the formation of a key tetrasubstituted carbon stereocenter, and the tetramic acid portion of the molecule can be accessed through silicon or boronic ester conjugate addition to an ene-lactam.
17BETA-HYDROXYSTEROID DEHYDROGENASE TYPE 1 INHIBITORS FOR THE TREATMENT OF HORMONE-RELATED DISEASES
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Page/Page column 13, (2010/08/18)
The invention relates to the use of non-steroidal 17beta-hydroxysteroid dehydrogenase type 1 inhibitors for the treatment and prophylaxis of hormone-dependent, particularly estrogen-dependent, diseases.The invention further relates to suitable inhibitors and to a method for the production thereof.
