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We describe a convenient method for the synthesis of multi-substituted allenes from SN2? substitution reactions organoaluminum with propargyl acetates: The SN2? substitution reaction of organoaluminum (0.4 mmol) with propargyl acetates (0.5 mmol) mediated by PdCl2(dppf) (1 mol%) at 60 C in THF without ligand could produce multi-substituted allenes in moderate to good yields (up to 98%) and high selectivities (up to 99%). Their structures have been determined by HRMS and 1H (13C)NMR data.

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

Brief introduction of Methanesulfonato(2-dicyclohexylphosphino-2′,4′,6′-tri-i-propyl-1,1′-biphenyl)(2′-amino-1,1′-biphenyl-2-yl)palladium(II)

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Chemistry is traditionally divided into organic and inorganic chemistry. Application In Synthesis of Methanesulfonato(2-dicyclohexylphosphino-2′,4′,6′-tri-i-propyl-1,1′-biphenyl)(2′-amino-1,1′-biphenyl-2-yl)palladium(II), The former is the study of compounds containing at least one carbon-hydrogen bonds.In a patent,Which mentioned a new discovery about 1445085-55-1

Iodomethylboron compounds, either the trifluoroborate or a boronic ester, cyclopropanate electron-rich olefins and unprotected allylic alcohols with Pd catalysts according to a novel, designed catalytic cycle. Proposed intermediates in a “diverted Heck” mechanism are observed by means of spectroscopic studies and by isolation and X-ray crystallographic characterization, which together with reaction kinetics point to a separation of rate-determining and product-determining steps, and a mechanism-based optimization of the yield, selectivity, and scope of the catalytic electrophilic cyclopropanation. The reaction with crystalline, air-stable, nonhygroscopic, and nontoxic reagents provides an alternative to Simmons-Smith-type reactions, as well as cyclopropanation procedures that require the use of diazomethane.

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

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Cationic water-soluble poly(fluorene-co-phenylene)s with electron withdrawing or donating substituents on the conjugated backbone were designed and synthesized. Fluorescence resonance energy transfer (FRET) experiments between these conjugated polymers and dye-labeled single-stranded DNA (ssDNA-C*) reveal the importance of matching donor and acceptor orbital energy levels to improve the sensitization of C* emission. Quenching of polymer fluorescence with ssDNA-C* and differences in C* emission suggest involvement of photoinduced charge transfer (PCT) as an energy wasting mechanism. The HOMO and LUMO energy levels of the conjugated polymers and C* serve as a preliminary basis to understand the competition between FRET and PCT. Dilution of C* in polymer/ssDNA-C* complexes by addition of ssDNA yields insight into C*…C* self-quenching. Under optimized conditions, where there is no probe self-quenching and minimum PCT, efficient signal amplification is demonstrated despite poor spectral overlap between polymer and C*.

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

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We report the optimization of a series of non-steroidal GR antagonists that led to the identification of compound 7. This compound is efficacious when dosed orally in an olanzapine-induced weight gain model in rats.

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

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Two different organometallic reagents now can cross-couple together with the oxidative cross-coupling strategy. Palladium catalyzed oxidative cross-couplings of alkylzinc and alkynylstannane reagents using desyl chloride as the oxidant have been explored, which produce the desired Csp-Csp3 cross-coupling product in surprisingly high selectivity and yields. The current catalytic system tolerates the presence of beta-H, and the reactions using long chain alkyl zinc reagents gave the cross-coupling product in excellent yields and selectivities. Copyright

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

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A novel one-pot, ?green? protocol to rapidly access pharmaceutically relevant heteroaryl methyl substrates is described. This process allows for a tandem SN2/Suzuki-Miyaura reaction or Sonogashira reaction across a breadth of chemical diversity with yields ranging between 31 and 87% for the tandem Suzuki-Miyaura process and 50?66% for the tandem Sonogashira process. This procedure tolerates S, N, and O heteroatom linkers and is amenable for both rapid and robust lead development screening. In addition, T-type and N-type calcium channel blocker (15) was synthesized in 43% yield using this methodology which stands as an improvement in both yield and reaction time of the previously reported synthesis. The one-pot protocol also allows for the inclusion of greater chemical diversity within the scaffold of 15.

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

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Overexpression and somatic heterozygous mutations of EZH2, the catalytic subunit of polycomb repressive complex 2 (PRC2), are associated with several tumor types. EZH2 inhibitor, EPZ-6438 (tazemetostat), demonstrated clinical efficacy in patients with acceptable safety profile as monotherapy. EED, another subunit of PRC2 complex, is essential for its histone methyltransferase activity through direct binding to trimethylated lysine 27 on histone 3 (H3K27Me3). Herein we disclose the discovery of a first-in-class potent, selective, and orally bioavailable EED inhibitor compound 43 (EED226). Guided by X-ray crystallography, compound 43 was discovered by fragmentation and regrowth of compound 7, a PRC2 HTS hit that directly binds EED. The ensuing scaffold hopping followed by multiparameter optimization led to the discovery of 43. Compound 43 induces robust and sustained tumor regression in EZH2MUT preclinical DLBCL model. For the first time we demonstrate that specific and direct inhibition of EED can be effective as an anticancer strategy.

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

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Functional supramolecular architectures for bottom-up organic nano- and microtechnology are a high priority research topic. We discovered a new recognition algorithm, resulting from the combination of thioalkyl substituents and head-to-head regiochemistry of substitution, to induce the spontaneous self-assembly of sulfur overrich octathiophenes into supramolecular crystalline fibers combining high charge mobility and intense fluorescence. The fibers were grown on various types of surfaces either as superhelices or straight rods depending on molecular structure. Helical fibers directly grown on a field effect transistor displayed efficient charge mobility and intrinsic ‘memory effect’. Despite the fact that the oligomers did not have chirality centers, one type of hand-helicity was always predominant in helical fibers, due to the interplay of molecular atropisomerism and supramolecular helicity induced by terminal substituents. Finally, we found that the new sulfur overrich oligothiophenes can easily be prepared in high yields through ultrasound and microwave assistance in green conditions.

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

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The syntheses, X-ray crystal structures, and molecular dynamics of 9-ferrocenylanthracene, 3, 9,10-diferrocenylanthracene, 4, 9- ferrocenyltriptycene, 7, and 9,10-diferrocenyltriptycene, 8, are reported. At 193 K, 3 exhibits Cs symmetry via oscillation of the ferrocenyl only about the anthracene plane; at higher temperatures, complete rotation about the C(9)-ferrocenyl linkage becomes evident with a barrier of 10.6 kcal mol -1. At 193 K, the ferrocenyls in 4 give rise to syn (C2v) and anti (C2h) rotamers that also interconvert at room temperature. In the corresponding triptycyl systems, 7 and 8, these rotational barriers increase to 17 kcal mol-1; 9,10-diferrocenyltriptycene exists as slowly interconverting meso and racemic rotamers, in which the ferrocenyl moieties are, respectively, eclipsed (C2v) or staggered (C 2). 2D-EXSY NMR data recorded with different mixing times indicate clearly that these interconversions proceed in a stepwise manner, for example, rac?meso?rac, thus behaving as a set of molecular dials.

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

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S1, 1 ‘-bis (diphenylphosphine) ferrocene dipalladium dichloride is added to a heating device, and the reaction liquid, 1, 1′ -bis (diphenylphosphine) ferrocene dipalladium dichloride is added to the extraction device. S2, and a heating device, a heating reflux 1, and an extraction device are added into the extraction solution after the reaction is finished; and S3, a heating device is added to the extraction solution and the extraction liquid is added into the flask, and stirred, and then the mixture 1 is stirred to obtain a 1’ . method, and a method for preparing the methylene dichloride 5 – 10 ml methylene chloride complex is obtained by the preparation method disclosed by the invention in the following step: 1. S4. 1 – 10h-bis (diphenylphosphine) ferrocene dipalladium chloride 1 complex crystal is obtained by adding an extracting 1 solution 1, and an extracting solution is added into the extraction device through a 0.8 1 condensation 1 – 1.2 pipe; and a heating device is obtained. The method comprises the steps: preparing a filter paper tube, and heating and refluxing the mixture. (by machine translation)

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