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Palladium-catalyzed incorporation of atmospheric CO2: Efficient synthesis of functionalized oxazolidinones

Methods to incorporate atmospheric CO2 into organic molecules are on demand. Here we present two Pd-catalyzed multicomponent reactions that provide functionalized oxazolidinones from propargylamines, aryl halides and CO2 as starting materials. These transformations, devoid of high CO2 pressures, represent a streamlined stereocontrolled synthesis of previously inaccessible versions of these useful heterocycles in an atom-economic manner, as up to four new single bonds are formed in a single synthetic operation.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Extracurricular laboratory:new discovery of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Topological Effects on Intramolecular Electron Transfer via Quantum Interference

The three isomers of diferrocenylbenzenes (ortho, 1o; meta, 1m; para, 1p) as well as 5-substituted derivatives of m-diferrocenylbenzene with R = NH2 (2), Cl (3), CH3 (4), CN (5), NO2 (6), and N(CH3)33+ (7) have been prepared. Crystal structures of 1o, 3, and 5 have been solved. In 3 and 5, the cyclopentadienyl rings are nearly parallel to the benzene mean planes with angles ranging from 9.99(5) to 14.74(5). One ferrocene group is above and the other below the mean molecular plane. For 1o, there is an important twist between the benzene and cyclopentadiene rings (68.6(8) and 32.5(8)) for steric reasons. Controlled potential electrolysis yields the mixed-valence ferrocene/ ferrocenium species in comproportionation equilibrium with homovalent species. Intervalence transitions have been observed and corrected from comproportionation. From the intervalence band parameters, metal-metal couplings (Vab) are calculated using Hush’s equation. The values are much higher for 1o (0.025 eV) and 1p (0.043 eV) than for 1m (0.012 eV) and exhibit little or no variation for the substituted m-diferrocenylbenzenes 2-6. These results are rationalized by extended Hueckel molecular orbital calculations. The weakness of the interaction in 1m can be ultimately traced to a quantum Interference effect, i.e., a cancellation of the contributions of two electron transfer paths. This cancellation occurs because each path implies a mixing of metal orbitals with a different ligand orbital, and the resulting molecular orbitals exhibit different symmetries.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Palladium-catalyzed aerobic oxidative carbonylation of arylboronate esters under mild conditions

(Figure Presented) “CO”n Air: The title reaction was carried out using [PdCl2(PPh3)2 ] as the catalyst precursor under very mild conditions (balloon pressure of CO and air, at 40- 50C), and produced a wide range of aryl carboxyl esters 2 in good to excellent yields. Remarkable selectivity between oxidative carbonylation and homocoupling of arylboronate esters l was also achieved.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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BICYCLIC HETEROCYCLIC DERIVATIVES AS MNK1 AND MNK2 MODULATORS AND USES THEREOF

The present invention relates to certain compounds (e.g., imidazopyrazine, imidazopyridine, imidazopyridazine and imidazpyrimidine compounds) that act as inhibitors of the MAP kinase interacting kinases MNK2a, MNK2b, MNK1a, and MNK1b. The present invention further relates to pharmaceutical compositions comprising these compounds, and to the use of the compounds for the preparation of a medicament for the prophylaxis and treatment of diseases (e.g., proliferative diseases (e.g., cancer), inflammatory diseases, Alzheimer’s disease), as well as methods of treating these diseases.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Atropisomeric 8-arylchromen-4-ones exhibit enantioselective inhibition of the DNA-dependent protein kinase (DNA-PK)

Substitution at the 3-position of the dibenzothiophen-4-yl ring of 8-(dibenzo[b,d]thiophen-4-yl)-2-morpholino-4H-chromen-4-one NU7441, a potent and selective DNA-dependent protein kinase (DNA-PK) inhibitor, with propyl, allyl or methyl enabled the separation by chiral HPLC of atropisomers. This is a consequence of restricted rotation about the dibenzothiophene-chromenone bond. Biological evaluation against DNA-PK of the pairs of atropisomers showed a marked difference in potency, with only one enantiomer being biologically active.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Palladium(II)/N,N-disubstituted-N?-acylthioureas complexes as anti-Mycobacterium tuberculosis and anti-Trypanosoma cruzi agents

The new complexes of Pd(II) with N,N-disubstituted-N?-acylthioureas:[(1) [Pd(dppf)(N,N-dimethyl-N?-benzoylthioureato-k2O,S)]PF6, (2) [Pd(dppf)(N,N-diethyl-N?-benzoylthioureato-k2O,S)]PF6, (3) [Pd(dppf)(N,N-dibuthyl-N?-benzoylthioureato-k2O,S)]PF6, (4) [Pd(dppf)(N,N-diphenyl-N?-benzoylthioureato-k2O,S)]PF6, (5) [Pd(dppf)(N,N-diethyl-N?-furoylthioureato-k2O,S)]PF6, (6) [Pd(dppf)(N,N-diphenyl-N?-furoylthioureato-k2O,S)]PF6, (7) [Pd(dppf)(N,N-dimethyl-N?- thiophenylthioureato-k2O,S)]PF6, and (8) [Pd(dppf)(N,N-diphenyl-N?-thiophenylthioureato-k2O,S)]PF6, were prepared and characterized by elemental analysis, and spectroscopic techniques. The structures of complexes (2), (3), (5), (6) and (8) had their structures determined by X-ray crystallography, confirming the coordination of the ligands with the metal through sulfur and oxygen atoms, forming distorted square-planar geometries. These complexes have shown antibacterial activity against anti-Mycobacterium tuberculosis H37Rv ATCC 27294. The complexes exhibited antiparasitic activity against Trypanosoma cruzi, while the metal-free thioureas did not. The results demonstrated that the compounds described here can be considered as promising anti-Mycobacterium tuberculosis and anti-T. cruzi agents, since in both cases their in vitro activity were better than reference drugs available for the treatment of both diseases.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Multimetallic complexes of group 10 and 11 metals based on polydentate dithiocarbamate ligands

The ligands KS2CN(Bz)CH2CH2N(Bz)CS 2K (K2L1), N(CH2CH 2N(Me)CS2Na)3 (Na3L2), and the new chelates {(CH2CH2)NCS2Na} 3 (Na3L3) and {CH2CH 2N(CS2Na)CH2CH2CH 2NCS2Na}2 (Na4L4), react with the gold(I) complexes [ClAu(PR3)] (R = Me, Ph, Cy) and [ClAu(IDip)] to yield di-, tri-and tetragold compounds. Larger metal units can also be coordinated by the longer, flexible linker, K2L1. Thus two equivalents of cis-[PtCl2(PEt3)2] react with K2L1 in the presence of NH4PF 6 to yield the bimetallic complex [L1{Pt(PEt 3)2}2](PF6)2. The compounds [NiCl2(dppp)] and [MCl2(dppf)] (M = Ni, Pd, Pt; dppp = 1,3-bis(diphenylphosphino)propane, dppf = 1,1′-bis(diphenylphosphino) ferrocene) also yield the dications, [L1{Ni(dppp)}2] 2+ and [L1{Ni(dppf)}2]2+ in an analogous fashion. In the same manner, reaction between [(L?2) (AuCl)2] (L?2 = dppm, dppf; dppm = bis(diphenylphosphino)methane) and KS2CN(Bz)CH2CH 2N(Bz)CS2K yield [L1{Au2(L? 2)}2]. The molecular structures of [L1{M(dppf)} 2](PF6)2 (M = Ni, Pd) and [L 1{Au(PR3)}2] (R = Me, Ph) are reported.

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Palladium/carbon catalyst regeneration and mechanical application method

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Carbonylation of aryl halides: Extending the scope of the reaction

Carbonylation reactions are being increasingly favoured in pharmaceutical chemistry for the atom-efficient introduction of carbonyl centres in aldehydes, acids, esters, and amides. Convenient procedures for simple aryl iodides and bromides are well established, and now the need is to develop improved conditions to allow the reactions to be extended to the more unreactive substrates, such as sterically hindered compounds and aryl chlorides. Sterically hindered compounds such as 2-iodo- or 2-bromo-m-xylenes can be converted using alkoxy and aminocarbonylation, while dehalogenation becomes a significant side reaction for reductive carbonylation. Less hindered compounds such as 2-iodo- or bromotoluene can be reacted successfully. Changing the aryl ligands of PdCl2{Ph2P(CH2)3PPh2} to alkyl groups improves the rate of oxidative addition but slows the carbonyl insertion step such that rates for the majority of aryl bromides are not improved by this change. Complexes such as PdCl2{Cy 2P(CH2)3PCy2} offer better performance for alkoxy and aminocarbonylation of aryl chlorides. However, for reductive carbonylation dehalogenation is a significant side reaction. Increasing CO pressure results in additional CO coordination to the catalytic intermediates and slows the reaction, while the dehalogenation is little affected, so reaction selectivity suffers. Thus, CO pressure is a critical parameter, particularly for reductive carbonylation, in achieving the optimum performance.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Synthesis and properties of conjugated copolymer having alternate structure of diphenylanthracene and allene

A conjugated copolymer having an alternate structure of 9,10-diphenylanthracene and 1,3-diphenylallene was synthesized by the Suzuki-Miyaura cross-coupling reaction with 9,10-dibororanylanthracene and 1,3-bis(4-bromophenyl)-1,3-diphenylallene. The diphenylanthracene moiety worked as an absorptive and emissive center unit in the polymer. The twisted allene moiety not only controlled conjugation length of the polymer but also suppressed formation of excimers, which realized intense pure blue fluorescence with high quantum efficiency (Phif ? 1.0) in CHCl3 solution. Copyright

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Formal Ir-Catalyzed Ligand-Enabled Ortho and Meta Borylation of Aromatic Aldehydes via in Situ-Generated Imines

The ligand-enabled development of ortho and meta C-H borylation of aromatic aldehydes is reported. It was envisaged that while ortho borylation could be achieved using tert-butylamine as the traceless protecting/directing group, meta borylation proceeds via an electrostatic interaction and a secondary interaction between the ligand of the catalyst and the substrate. These ligand-substrate electrostatic interactions and secondary B-N interactions provide an unprecedented controlling factor for meta-selective C-H activation/borylation.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method