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Sulfur-heterocycles are found in nature and they are recognized by biological systems as effective pharmacophores inducing anticancer, antimicrobial, antiviral, anti-diabetic activities via e.g. blocking functionality of many enzymes and receptors. Due to the biological importance of sulfur heterocycles, novel and efficient synthetic strategies, opening the access to regio- and stereoselective construction and functionalization of these scaffolds are in high demand. The advantages and some limitations of tandem strategies are discussed in view of challenges related to the construction of adequately functionalized or fused main heterocyclic sulfur frameworks of biological interest. In addition, examples of sulfur-heterocycles of important biological potency as well as domino reaction mechanisms revealing novel possibilities and ideas for construction of these attractive molecules, are reviewed. Bibliography presented in this review contains references to papers, which appeared mainly during the period from 2009 to 2018.

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

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New drugs introduced to the market every year represent privileged structures for particular biological targets. These new chemical entities (NCEs) provide insight into molecular recognition and also serve as leads for designing future new drugs. This annual review covers the synthesis of thirty-seven NCEs that were approved for the first time in 2014 and one drug which was approved in 2013 and was not covered in a previous edition of this review.

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

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Novel heteroleptic iridium complexes are disclosed. The complexes contain a phenyl pyridine ligand and another ligand containing a dibenzofuran, dibenzothiophene, dibenzoselenophene, or carbazole linked to an imidazole or benzimidazole fragment. These complexes are useful materials when incorporated into OLED devices.

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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 facile synthesis of gamma,delta-unsaturated ketones via palladium-catalyzed ring-opening of 2-alkylidenecyclobutanols with organic halides is described. The key step involves Csp3 ? Csp2 bond cleavage via palladium-catalyzed beta-carbon elimination. The desired gamma,delta-unsaturated ketones are obtained in good to excellent yields and broad functional group tolerability. Aryl, heteroaryl, benzyl, and alkynyl halides all readily participate to forge tri-substituted carbon-carbon double bond in a stereoselective manner. (Figure presented.).

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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 present application relates to active compound combinations of pyrazin-2-ylpyrazoles (component A) with at least one further ectoparasiticide or synergists (component B), and to products comprising such active compound combinations. These active compound combinations are suitable for controlling animal pests in the field of veterinary medicine.

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

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Syntheses of 1,2-, 1,3-, 1,4-, 1,8-, 2,4-, 3,4-, 4,8-, 1,2,4-, 1,2,8- and 1,3,4-functionalized dibenzofurans in few steps with good to excellent yields starting from dibenzofuran-1-ol or -4-ol are presented. These rapidly accessible bi- or tri-functionalized building blocks are of great interest for the synthesis of bioactive substances or functional material development. Furthermore, for intermediates containing both a bromine and a triflate moiety, a selective mono-substitution by means of Suzuki?Miyaura reaction (SMR) is described.

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

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Current methods for functional group interconversion have, for the most part, relied on relatively strong driving forces which often require highly reactive reagents to generate irreversibly a desired product in high yield and selectivity. These approaches generally prevent the use of the same catalytic strategy to perform the reverse reaction. Here we describe a catalytic functional group metathesis approach to interconvert, under CO-free conditions, two synthetically important classes of electrophiles that are often employed in the preparation of pharmaceuticals and agrochemicals?aroyl chlorides (ArCOCl) and aryl iodides (ArI). Our reaction design relies on the implementation of a key reversible ligand C?P bond cleavage event, which enables a non-innocent, metathesis-active phosphine ligand to mediate a rapid aryl group transfer between the two different electrophiles. Beyond enabling a practical and safer approach to the interconversion of ArCOCl and ArI, this type of ligand non-innocence provides a blueprint for the development of a broad range of functional group metathesis reactions employing synthetically relevant aryl electrophiles.

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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 hydrogenolysis of mono- and dinuclear PdII hydroxides was investigated both experimentally and computationally. It was found that the dinuclear mu-hydroxide complexes {[(PCNR)Pd]2(mu-OH)}(OTf) (PCNH=1-[3-[(di-tert-butylphosphino)methyl]phenyl]-1H-pyrazole; PCNMe=1-[3-[(di-tert-butylphosphino)methyl]phenyl]-5-methyl-1H-pyrazole) react with H2 to form the analogous dinuclear hydride species {[(PCNR)Pd]2(mu-H)}(OTf). The dinuclear mu-hydride complexes were fully characterized, and are rare examples of structurally characterized unsupported singly bridged mu-H PdII dimers. The {[(PCNMe)Pd]2(mu-OH)}(OTf) hydrogenolysis mechanism was investigated through experiments and computations. The hydrogenolysis of the mononuclear complex (PCNH)Pd-OH resulted in a mixed ligand dinuclear species [(PCNH)Pd](mu-H)[(PCC)Pd] (PCC=a dianionic version of PCNH bound through phosphorus P, aryl C, and pyrazole C atoms) generated from initial ligand ?rollover? C?H activation. Further exposure to H2 yields the bisphosphine Pd0 complex Pd[(H)PCNH]2. When the ligand was protected at the pyrazole 5-position in the (PCNMe)Pd?OH complex, no hydride formed under the same conditions; the reaction proceeded directly to the bisphosphine Pd0 complex Pd[(H)PCNMe]2. Reaction mechanisms for the hydrogenolysis of the monomeric and dimeric hydroxides are proposed.

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

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There are provided novel compounds of formula (I) 1wherein R1, R2, R3, X and Z are as defined in the Specification and optical isomers, racemates and tautomers thereof and pharmaceutically acceptable salts thereof; together with processes for their preparation, compositions containing them and their use in therapy. The compounds are inhibitors of the enzyme nitric oxide synthase.

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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 new approach to the synthesis of benzothiophene-based palladium(II) complex of SCN unsymmetrical pincer-type ligand from iodocyclization of bis(methylthio)phenyl substituted ethynyl pyridine followed by oxidative addition of tris-(dibenzyledeneacetone) dipalladium(0) has been developed. The mechanistic implication of palladium complex reveals the practical evidence of oxidative addition step in Suzuki coupling reaction.

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