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Visible-light mediated aerobic dehydrogenation of N-heterocyclic compounds is a reaction with enormous potential for application. Herein, we report the first complete aerobic dehydrogenation pathway to large-scale production of isoquinolines. The discovery of this visible light photoredox reaction was enabled through the combination of mathematical simulations and real-time quantitative mass spectrometry screening. The theoretical calculations showed that hyper-conjugation, the main underlying factor hindering the aerobic oxidation of tetrahydroisoquinolines, is relieved both by pi- and sigma-donating substituents. This mechanistic insight provided a novel photocatalytic route based on N-substituted auxiliaries that facilitated the conversion of tetrahydroisoquinolines into the corresponding isoquinolines in just three simple steps (yield 71.7% in bulk-solution phase), using unmodified Ru(bpy)3Cl2 photocatalyst, sun energy, atmospheric O2, and at ambient temperature.

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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 di-cyanovinyl-based small molecules were successfully used as non-fullerene acceptors in high-performance organic solar cells. However, the field-effect performances of these types of small molecules are still rarely studied. In this paper, two acceptor-donor-acceptor (A?D?A) small molecules with fuse ring as donor and strong electron-withdrawing 2-(2-oxindolin-3-ylidene)malononitrile derivatives as acceptors were synthesized and characterized for use in solution-processed organic field-effect transistors (OFETs). The new molecules had deep lowest unoccupied molecular orbital energy level (? ?4.0 eV) for marching the electron transport and exhibited n-type charge transport characteristics. The OFETs based on the small molecules exhibited the highest electron mobility of over 3 × 10?3 cm2V?1s?1. This work indicates that di-cyanovinyl-based small molecules can also be applied in n-type OFETs.

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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 preparation of bimetallic nanoparticles with controlled size, shape, and composition remains a difficult task, and reproducible methods are highly desired. Here, we report the codecomposition of Ni(cod)2 and Pd 2(dba)3 organometallic precursors in the presence of hexadecylamine (HDA) and hydrogen as an efficient approach to get size-controlled bimetallic nickel-palladium nanoparticles. Presynthesized nickel-palladium nanoparticles of different Ni/Pd ratios were further used for the preparation of supported catalysts by the sol-immobilization method onto a magnetic silica. The obtained supported catalysts were investigated in the hydrogenation of cyclohexene and compared to Ni and Pd monometallic catalysts. The catalysts prepared with a 1:9 Ni/Pd molar ratio achieved the highest initial turnover frequency > 50000 h-1, providing higher activity than the pure Pd monometallic counterpart. This represents an important saving of noble metal. Moreover, the magnetic separation allows excellent separation of the catalyst from the liquid products without metal leaching and exposure to air, leading to an efficient recycling.

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

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Highly Enantioselective [5 + 2] Annulations through Cooperative N-Heterocyclic Carbene (NHC) Organocatalysis and Palladium Catalysis

The highly enantioselective [5 + 2] annulation of enals with vinylethylene carbonates through a cooperative N-heterocyclic carbene (NHC)/Pd catalytic system is reported. The use of a bidentate phosphine ligand was crucial to prevent coordination of the NHC organocatalyst to the active Pd catalyst. The complementary and matched combination of the chiral NHC catalyst and chiral phosphine ligand promotes high levels of both reactivity and enantioselectivity (mostly ?99% ee).

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

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Hydroarylation of 2-Aryloxybut-1-en-3-ynes via Pd/Acid-Catalyzed C?H Bond Activation: A Concise Synthesis of 2,3-Bismethylene-2,3-dihydrobenzofurans

An intramolecular exo-hydroarylation of 2-aryloxy-1,4-disilylbut-1-en-3-ynes via ortho-C?H bond activation under palladium(0) and acid catalysis was found to give 2,3-bis(silylmethylidene)-2,3-dihydrobenzofurans. The two silyl groups present probably promoted the reaction and played a key role in stabilizing the diene moiety in the product. The products readily led to functionalized condensed cycles by a Diels?Alder reaction.

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

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USE OF SPIRO-OXINDOLE COMPOUNDS AS THERAPEUTIC AGENTS

This invention is directed to methods of using spiro-oxindole compounds of formula (I): wherein k, j, Q, R1, R2a, R2b, R2c, R2d, R3a, R3b, R3c, and R3d are as defined herein, as a stereoisomer, enantiomer, tautomer thereof or mixtures thereof; or a pharmaceutically acceptable salt, solvate or prodrug thereof, for the treatment and/or prevention of hypercholesterolemia, benign prostatic hyperplasia, pruritis and cancer.

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

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Pd0-mediated rapid coupling of methyl iodide with excess amounts of benzyl- and cinnamylboronic acid esters: Efficient method for incorporation of positron-emitting 11C radionuclide into organic frameworks by coupling between two sp3-hybridized carbons

Pd0-mediated rapid cross coupling between sp3- hybridized carbons of CH3I and benzyl- or cinnamylboronic acid esters using [Pd{P(tert-C4H9)3}2]/CsF in DMF/H2O gave the corresponding methylated compounds in high yield. The utility was well demonstrated for the synthesis of short-lived PET tracer, N-(4-[11C]ethylphenyl)propionamide, in 90 ± 1% radio-HPLC analytical yield and 49 ± 3% radiochemical yield.

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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 Simply Synthesized, Tough Polyarylene with Transient Mechanochromic Response

A simple and high-yielding route to tough polyarylenes of the type poly(meta,meta,para-phenylene) (PmmpP) is developed. PmmpP is tough even in its as-synthesized state which has an intermediate molar mass of Mw?60 kg mol?1 and exhibits outstanding mechanical properties at further optimized molecular weight of Mw=96 kg mol?1, E=0.9 GPa, ?=300 %. Statistical copolymers with para,para-spiropyran (SP) are mechanochromic, and the toughness allows mechanochromism to be investigated. Strained samples instantaneously lose color upon force release. DFT calculations show this phenomenon to be caused by the PmmpP matrix that allows build-up of sufficiently large forces to be transduced to SP, and the relatively unstable corresponding merocyanine (MC) form arising from the aromatic co-monomer. MC units covalently incorporated into PmmpP show a drastically reduced half life time of 3.1 s compared to 4.5 h obtained for SP derivatives with common 6-nitro substitution.

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

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Synthesis of 1,1-Disubstituted Indenes and Dihydronaphthalenes through C-C/C-C Bond-Forming Pd-Catalyzed Autotandem Reactions

A novel synthesis of 1,1-disubstituted 1H-indenes is described involving the Pd-catalyzed cascade reaction between o-bromophenyl-beta-bromostyrenes and N-tosylhydrazones in a process comprising the consecutive formation of two Csp3-C bonds on the same carbon atom: the cross-coupling of the N-tosylhydrazone with the alkenyl bromide and the intramolecular Heck reaction on the newly formed double bond. A similar approach has been applied to the preparation of 1,1-disubstituted naphthalenes.

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

Brief introduction of Pd2(DBA)3

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Palladium(0)-Catalyzed Directed syn-1,2-Carboboration and -Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary

We report the development of palladium(0)-catalyzed syn-selective 1,2-carboboration and -silylation reactions of alkenes containing cleavable directing groups. With B2pin2 or PhMe2Si-Bpin as nucleophiles and aryl/alkenyl triflates as electrophiles, a broad range of mono-, di-, tri- and tetrasubstituted alkenes are compatible in these transformations. We further describe a directed dearomative 1,2-carboboration of electron-rich heteroarenes by employing this approach. Through use of a removable chiral directing group, we demonstrate the viability of achieving stereoinduction in Heck-type alkene 1,2-difunctionalization. This work introduces new avenues to access highly functionalized boronates and silanes with precise regio- and stereocontrol.

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