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Summary: Palladium-catalyzed reactions of unsaturated organozincs with aryl or alkenyl iodides can exhibit turnover numbers (TONs) over 105 (>70% product yields). Under the conditions employed, Zn, B, and In appear to be the three most favorable metals, followed by Al(Zn) and Zr(Zn), whereas TONs observable with Sn, Cu, and Mn have been significantly lower.

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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 highly enantio- and regioselective copper catalyzed asymmetric propargylation of aldehydes with a propargyl borolane reagent is reported. The methodology demonstrated broad functional group tolerance and provided high enantioselectivities for aliphatic, vinyl, and aryl aldehydes. The utility of the TMS homopropargylic alcohols was demonstrated by the facile conversion to a chiral dihydropyranone.

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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 process for preparing cyclopentadiene derivatives having formula (I) wherein T1 is selected from the group consisting of oxygen (O), or sulphur (S); R1, R2, R3 an d R4, are hydrogen atoms, or hydrocarbon radicals; comprising the following steps: a) reacting a compound of formula (II) with a compound of formula (III) in the presence of a palladium or nickel based catalyst and a base; b) contacting the obtained compound with a carbonylating system; and c) treating the product obtained in step b) with a reducing agent.

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

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Total synthesis of structurally complex marine oxacyclic natural products, (-)-gambierol, (-)-brevenal, and (+)-neopeltolide, has been accomplished by exploiting SuzukiMiyaura coupling of enol phosphates, paving the way for biological investigations on these scarcely available substances.

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

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An efficient method for the synthesis of 6-alkyl or 6-aryl purines (nucleosides) was developed via nickel-catalyzed Negishi cross-couplings of 6-chloropurines and organozinc halides. The ligand-free process gave good to excellent isolated yields at room 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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Control over generation and dynamics of excited electronic states is fundamental to their utilization in all areas of technology. We present the first example of multichromophoric systems in which emissive triplet states are generated via a pathway involving photoinduced electron transfer (ET), as opposed to local intrachromophoric processes. In model dyads, PtP-Ph n-pRhB+ (1-3, n = 1-3), comprising platinum(II) meso-tetraarylporphyrin (PtP) and Rhodamine B piperazine derivative (pRhB +), linked by oligo-p-phenylene bridges (Phn), upon selective excitation of pRhB+ at a frequency below that of the lowest allowed transition of PtP, room-temperature T1?S0 phosphorescence of PtP was observed. The pathway leading to the emissive PtP triplet state includes excitation of pRhB+, ET with formation of the singlet radical pair, intersystem crossing within that pair, and subsequent radical recombination. Because of the close proximity of the triplet energy levels of PtP and pRhB+, reversible triplet-triplet (TT) energy transfer between these states was observed in dyads 1 and 2. As a result, the phosphorescence of PtP was extended in time by the long decay of the pRhB + triplet. Observation of ET and TT in the same series of molecules enabled direct comparison of the distance attenuation factors I between these two closely related processes.

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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 provide efficient synthetic access to heteroaryl sulfones in two-steps using a simple palladium?1,1?-bis[(diphenyl)phosphanyl]ferrocene catalyst to form in high yields variously functionalized heteroaromatic thioethers. Pyridinyl-containing substrates can be subsequently selectively oxidized into sulfones and NH-sulfoximines by using very mild oxidation conditions with a high functional group tolerance. In the palladium-catalyzed C?S coupling of heteroaromatic thiols, reactivity limitation is attached with electron-deficient thiols. We show that this limitation can be resolved by the successful use of 2-bromoheteroarenes in the C?S coupling. We established herein that this choice of heteroaryl electrophilic reagent in palladium-catalyzed C?S bond formation allows overcoming palladium dithiolate out-of-cycle resting state inertness. This was illustrated in the stoichiometric reactivity study of the palladium dithiolate formed from 4-trifluoromethylbenzen-1-thiol ?isolated and characterized by multinuclear NMR and XRD? with both 2-chloropyridine and 2-bromopyridine.

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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 invention discloses a 2 – bit thienyl substituted asymmetric fluorine boron complexed pyrrole methine (BODIPY) derivative and its preparation method. It has the structure of formula I, which comprises a 2 – bit thienyl substituted beryllium complex two-pyrrole-methine respectively […], carbazole and triphenylamine and electronic group for the coupling reaction. Such non-symmetric beryllium complex two-pyrrole-methine derivatives compared with BODIPY precursor of the ultraviolet absorption is obviously red shift phenomenon, its fluorescence emission peak tends to near-infrared region; and the synthetic method is simple, easy to control, higher yield, has universality. The invention leads the BODIPY dye can be and is widely used in the efficient synthesis of the fluorescent dye, the light-emitting material, the photovoltaic material, life science, analytical science, environmental energy science, organic solar cell battery. (by machine translation)

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

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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 growing threat of untreatable bacterial infections has refocused efforts to identify new antibiotics, especially those acting by novel mechanisms. While the inhibition of pathogen proteases has proven to be a successful strategy for drug development, such inhibitors are often limited by toxicity due to their promiscuous inhibition of homologous and mechanistically related human enzymes. Unlike many protease inhibitors, inhibitors of the essential type I bacterial signal peptidase (SPase) may be more specific and thus less toxic due to the enzyme’s unique structure and catalytic mechanism. Recently, the arylomycins and related lipoglycopeptide natural products were isolated and shown to inhibit SPase. The core structure of the arylomycins and lipoglycopeptides consists of a biaryl-linked, N-methylated peptide macrocycle attached to a lipopeptide tail, and in the case of the lipoglycopeptides, a deoxymannose moiety. Herein, we report the first total synthesis of a member of this group of antibiotics, arylomycin A2. The synthesis relies on Suzuki-Miyaura-mediated biaryl coupling, which model studies suggested would be more efficient than a lactamization-based route. Biological studies demonstrate that these compounds are promising antibiotics, especially against Gram-positive pathogens, with activity against S. epidermidis that equals that of the currently prescribed antibiotics. Structural and biological studies suggest that both N-methylation and lipidation may contribute to antibiotic activity, whereas glycosylation appears to be generally less critical. Thus, these studies help identify the determinants of the biological activity of arylomycin A 2 and should aid in the design of analogs to further explore and develop this novel class of antibiotic.

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