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Pd-Catalyzed Hydroamination of Alkoxyallenes with Azole Heterocycles: Examples and Mechanistic Proposal

Palladium-catalyzed regio- and enantioselective addition of azole heterocycles to alkoxyallenes was developed (up to 92% yields and up to 94% ee). DFT calculations suggest a new Pd(0)-driven mechanistic pathway proceeding through protonation of the Pd-coordinated allene (4-PdL2), which develops a strongly nucleophilic character at the central C atom.

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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 enantioselective Heck alkenylation of trisubstituted allylic alkenols: a redox-relay strategy to construct vicinal stereocenters

An enantioselective, redox-relay Heck alkenylation of trisubstituted allylic alkenol substrates has been developed. This process enables the construction of vicinal stereocenters in high diastereo- and enantioselectivity and allows the formation of enolizable alpha-carbonyl methyl-substituted stereocenters with no observed epimerization under the reported reaction conditions.

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

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Synthesis, Structure, and Catalysis of Palladium Complexes Bearing a Group 13 Metalloligand: Remarkable Effect of an Aluminum-Metalloligand in Hydrosilylation of CO2

Efficient synthesis and catalysis of a series of palladium complexes having a group 13 metalloligand (Al, Ga, In) are reported utilizing 6,6-bis(phosphino)terpyridine as a new scaffold for Pd-E bonds (E = Al, Ga, In). Systematic investigation revealed unique characteristics of the Al-metalloligand in both structure and reactivity, which exhibited the highest catalytic activity for hydrosilylation of CO2 ever reported (TOF = 19 300 h-1). This study demonstrated fine-tuning of catalyst activity by the precisely designed metalloligand is a promising approach for new catalyst development in synthetic organometallic chemistry.

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

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Late-stage functionalization of 1,2-dihydro-1,2-azaborines via regioselective iridium-catalyzed C-H borylation: The development of a new N,N-bidentate ligand scaffold

The first general late-stage functionalization of monocyclic 1,2-azaborines at the C(6) position is described. Ir-catalyzed C-H borylation occurs regioselectively at the C(6) position of B-substituted 1,2-azaborines and is compatible with a range of substitution patterns at boron (e.g., hydride, alkoxide, alkyl, and aryl substituents). Subsequent Suzuki cross coupling with aryl- and heteroaryl bromides furnishes 1,2-azaborine-based biaryl compounds including 6-[pyrid-2-yl]-1,2-azaborines that represent novel kappa2-N,N-bidentate ligands. The 6-[pyrid-2-yl]-B-Me-1,2-azaborine ligand has been demonstrated to form an emissive coordination complex with dimesitylboron that exhibits bathochromically shifted absorption and emission maxima and a higher photoluminescence quantum yield compared to its carbonaceous analogue.

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

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OXABICYCLO [2.2.2] ACID GPR120 MODULATORS

The present invention provides compounds of Formula (I): or a stereoisomer, or a pharmaceutically acceptable salt thereof, wherein all of the variables are as defined herein. These compounds are GPR120 G protein-coupled receptor modulators which may be used as medicaments.

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

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Carbon-Phosphorus Bond Formation by Enantioselective Palladium-Catalyzed Allylation of Diphenylphosphine Oxide

The enantioselective Pd-catalyzed allylation of diaryl-substituted allylic carbonates and diphenylphosphine oxide was investigated. This method gave allylic diphenylphosphine oxides in yields up to 95 % with 97 % ee. Pd-catalyzed allylation of (E)-methyl allyl carbonates with diisopropyl phosphonate was also examined. The Pd-catalyzed asymmetric allylation of diphenylphosphine oxide to form P-allylated products in yields up to 95 % with 97 % ee is described. Pd-catalyzed allylation of (E)-methyl allyl carbonates with diisopropyl phosphonate is accomplished, which regioselectively gives linear P-allylated products in 65-95 % yields; BINAP = 2,2?-bis(diphenylphosphino)-1,1?-binaphthyl.

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

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Radiosynthesis of carbon-11 labeled 6-methyldopamine ([11C]MeDA)

A rapid and efficient n.c.a. radiosynthesis of 6-[11C]methyldopamine ([11C]MeDA) using the Stille cross-coupling reaction as a key step was developed. The labeling conditions for the formation of the intermediate compound (protected [11C]MeDA, [11C]7) were determined with respect to reaction temperature and time. The radiochemical yield 89¡À1.4% (decay-corrected) of the protected intermediate [11C]7 was obtained at a reaction temperature of 60C and a reaction time of 5min using Pd2(dba)3/P(o-tolyl)3 and CsF/CuBr as a co-catalyst system. The overall yield after deprotection with 45% HBr at 140C for 10min was 64¡À3.9% (decay-corrected) within a total preparation time of 40min, including hydrolysis, HPLC purification and formulation.

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

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Experimental and theoretical investigations on the optical and electrochemical properties of pi-conjugated donor-acceptor-donor (DAD) compounds toward a universal model

A series of nine (9) donor-acceptor-donor (DAD) pi-conjugated small molecules were synthesized via palladium catalyzed Stille aromatic cross-coupling reactions by the combination of six (6) heterocycle building blocks (thiophene, furan, thiazole, 2,1,3-benzothiadiazole, 2,1,3-pyridinothiadiazole, thienothiadiazole) acting as electron donating (thiazole, furan, thiophene) and electron deficient (benzothiadiazole, pyridinethiadiazole, thienothiadiazole) units. These model compounds enable determining the correspondence between the theoretical and experimental optical and electrochemical properties for the first time, via Density Functional Theory (DFT), time-dependent DFT, UV-Vis spectroscopy, and cyclic voltammetry, accordingly. The obtained theoretical models can be utilized for the design and synthesis of new DAD structures with precise optical bandgaps, absorption maxima, and energy levels suitable for different optoelectronic applications.

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

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An efficient route to highly strained cyclobutenes: Indium-catalyzed reactions of enynals with alkynes

A catalytic method to synthesize the highly strained cyclobutene was developed. The reaction was believed to proceed through a formal indium-catalyzed [2+2] cycloaddition between electron-deficient enynals and various alkynes. This journal is

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

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NOVEL HETEROCYCLIC COMPOUNDS AND USES THEREOF

New substituted heterocyclic compounds, compositions con?taining them, and methods of using them for the inhibition of Raf kinase activity are provided. The new compounds and compositions may be used either alone or in combination with at least one additional agent for the treatment of a Raf kinase mediated disorder, such as cancer

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