- Sulfoxide ligand metal catalyzed oxidation of olefins
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The enantioselective synthesis of isochroman motifs has been accomplished via Pd(II)-catalyzed allylic C—H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C—H oxidation reaction proceeds with the broadest scope and highest levels asymmetric induction reported to date (avg. 92% ee, 13 examples ≥90% ee). Additionally, C(sp3)-N fragment coupling reaction between abundant terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/sulfoxide (SOX) catalyzed intermolecular allylic C—H amination is disclosed. A range of 52 allylic amines are furnished in good yields (avg. 76%) and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E:Z). For the first time, a variety of singly activated aromatic and aliphatic nitrogen nucleophiles, including ones with stereochemical elements, can be used in fragment coupling stiochiometries for intermolecular C—H amination reactions.
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- Discovery of Novel Naphthylphenylketone and Naphthylphenylamine Derivatives as Cell Division Cycle 25B (CDC25B) Phosphatase Inhibitors: Design, Synthesis, Inhibition Mechanism, and in Vitro Efficacy against Melanoma Cell Lines
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CDC25 phosphatases play a critical role in the regulation of the cell cycle and thus represent attractive cancer therapeutic targets. We previously discovered the 4-(2-carboxybenzoyl)phthalic acid (NSC28620) as a new CDC25 inhibitor endowed with promising anticancer activity in breast, prostate, and leukemia cells. Herein, we report a structure-based optimization of NSC28620, leading to the identification of a series of novel naphthylphenylketone and naphthylphenylamine derivatives as CDC25B inhibitors. Compounds 7j, 7i, 6e, 7f, and 3 showed higher inhibitory activity than the initial lead, with Ki values in the low micromolar range. Kinetic analysis, intrinsic fluorescence studies, and induced fit docking simulations provided a mechanistic understanding of the activity of these derivatives. All compounds were tested in the highly aggressive human melanoma cell lines A2058 and A375. Compound 4a potently inhibited cell proliferation and colony formation, causing an increase of the G2/M phase and a reduction of the G0/G1 phase of the cell cycle in both cell lines.
- Cerchia, Carmen,Nasso, Rosarita,Mori, Matteo,Villa, Stefania,Gelain, Arianna,Capasso, Alessandra,Aliotta, Federica,Simonetti, Martina,Rullo, Rosario,Masullo, Mariorosario,De Vendittis, Emmanuele,Ruocco, Maria Rosaria,Lavecchia, Antonio
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p. 7089 - 7110
(2019/08/20)
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- C-H to C-N Cross-Coupling of Sulfonamides with Olefins
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Cross-coupling of nitrogen with hydrocarbons under fragment coupling conditions stands to significantly impact chemical synthesis. Herein, we disclose a C(sp3)-N fragment coupling reaction between terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/SOX (sulfoxide-oxazoline) catalyzed intermolecular allylic C-H amination. A range of (56) allylic amines are furnished in good yields (avg. 75%) and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E:Z). Mechanistic studies reveal that the SOX ligand framework is effective at promoting functionalization by supporting cationic π-allyl Pd.
- Ma, Rulin,Christina White
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p. 3202 - 3205
(2018/03/13)
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- Palladium-catalyzed electrophilic C–H fluorination of arenes using oxazoline as a removable directing group
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Dimethyloxazoline was rationally designed to act as a removable ortho-directing group (DG) for the palladium-catalyzed C–H electrophilic fluorination of arenes. Using NFSI as the fluorinating agent, and Pd(II), Ag(I) catalytic system, electrophilic C(sp2–H) ortho-fluorination took place on a variety of aryl substrates to afford the corresponding mono- and di-fluorinated products.
- Gutierrez, David A.,Lee, Wan-Chen Cindy,Shen, Yuning,Li, Jie Jack
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p. 5372 - 5376
(2016/11/11)
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- Bidentate cycloimidate palladium complexes with aliphatic and aromatic anagostic bonds
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Palladium(ii) complexes of bidentate cycloimidate ligand systems with a triarylmethyl moiety exhibit exceptional downfield shifts in proton NMR spectra due to rare anagostic interactions. This journal is the Partner Organisations 2014.
- Sch?ler, Stephan,Wahl, Maike H.,Wurster, Nicole I. C.,Puls, Arik,H?ttig, Christof,Dyker, Gerald
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p. 5909 - 5911
(2014/05/20)
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- Synthesis of 4-oxazolinephenylboronic acid and heterobiaryl oxazolines via a Suzuki reaction
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An efficient synthesis of 4-oxazolinephenylboronic acid from 4-bromobenzoic acid is reported. The title compound couples with heteroaryl halides in presence of Pd(PPh3)4 and Na2CO3 in aqueous toluene to give het
- Ghosh, Samir,Kumar, A.Sanjeev,Mehta,Soundararajan,Sen, Subhabrata
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scheme or table
p. 205 - 207
(2009/11/30)
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- Nickel(II) complexes bearing phosphinooxazoline ligands: Synthesis, structures and their ethylene oligomerization behaviors
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A series of Ni(II) complexes 4a-f ligated by the unsymmetrical phosphino-oxazolines (PHOX) were synthesized and characterized by elemental analysis and IR spectroscopy, and the structures of complexes 4c-4e were confirmed by the X-ray crystallographic analysis. All derivatives showed distorted tetrahedron geometry by the nickel center and coordinative atoms. Upon activation with methylaluminoxane (MAO) or Et2AlCl, these complexes exhibited considerable to high activity of ethylene oligomerization. The ligands environments and reaction conditions significantly affect their catalytic activities, while the highest oligomerization activity (up to 1.18 × 106 g ? mol-1(Ni) ? h-1) was observed for 4d at 20 atm of ethylene. Incorporation of 2-4 equivalents of PPh 3 as auxiliary ligands in the 4a-f/MAO catalytic systems led to higher activity and longer catalytic lifetime.
- Tang, Xiubo,Zhang, Dongheng,Jie, Suyun,Sun, Wen-Hua,Chen, Jiutong
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p. 3918 - 3928
(2007/10/03)
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- Substituted 1,3-dihydrospiro(isobenzofuran)s
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Novel substituted 1,3-dihydrospiro[isobenzofuran]s and methods of preparing the same are described. These compounds are useful as antidepressants, tranquilizers, analgetic agents and intermediates therefor.
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- 1,3-Dihydrospiro[isobenzofuran]s and derivatives thereof
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Novel substituted 1,3-dihydrospiro[isobenzofuran]s and methods of preparing the same are described. These compounds are useful as tranquilizers, analgetic agents and intermediates therefor.
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