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Pd-catalyzed cascade allylic alkylation and dearomatization reactions of indoles with vinyloxirane

We have developed Pd-catalyzed intermolecular Friedel-Crafts-type allylic alkylation and allylic dearomatization reactions of substituted indoles bearing a nucleophilic group with vinyloxirane, providing an efficient method to synthesize structurally diverse tetrahydrocarboline and spiroindolenine derivatives under mild conditions.

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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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Alkynyl?B(dan)s in Various Palladium-Catalyzed Carbon?Carbon Bond-Forming Reactions Leading to Internal Alkynes, 1,4-Enynes, Ynones, and Multiply Substituted Alkenes

It was found that the C(sp)?B(dan) bond of alkynyl?B(dan)s can be directly used for palladium-catalyzed carbon?carbon bond-forming reactions with aryl(alkenyl) halides and allylic carbonates as electrophiles, thus delivering unsymmetrical internal alkynes and unconjugated 1,4-enynes, respectively. With acyl chlorides as electrophiles, ynone synthesis is also promoted by a palladium catalyst with the assistance of a copper co-catalyst. These reactions can be achieved as more convenient one-pot reactions, without isolating the alkynyl?B(dan) formed in situ by the zinc-catalyzed dehydrogenative borylation of alkynes with HB(dan). In addition to direct C(sp)?B(dan) bond transformations, the C?C bond in an alkynyl?B(dan) proved to be a promising scaffold for the construction of a multisubstituted alkene, which is synthesized by diboration of the C?C?B(dan) moiety, leading to a triborylalkene followed by iterative regio- and stereoselective Suzuki?Miyaura cross-coupling reactions. As one example, the synthesis of the ethene with four different aryl groups, p-MeC6H4, p-MeOC6H4, p-NCC6H4, and p-F3CC6H4, was attained in high overall yield of 64% in six steps starting from the terminal alkyne, p-MeC6H4C?CH. Besides these synthetic applications of the alkynyl?B(dan), the scope of the alkynyl substrate in the zinc-catalyzed dehydrogenative borylation was expanded to enhance the reliability as a provider of the alkynyl?B(dan). Consequently, 42 alkynes were found to participate in the dehydrogenative borylation as substrates; these are alkyl-, alkenyl-, aryl-, heteroaryl-, ferrocenyl-, silyl-, and borylalkynes, with or without a variety of functional groups. Lastly, a new method for preparing HB(dan), as a sulfide-free, cost-saving, and reaction-time-saving route, is disclosed. (Figure presented.).

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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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Effect of heterocycles on field-effect transistor performances of donor-acceptor-donor type small molecules

Two D?A?D small molecules comprising triphenylamine and diketopyrrolopyrrole were synthesized having either furan or thiophene connected to the fused lactam ring. In this design, furan/thiophene diketopyrrolopyrrole acts as an acceptor and triphenylamine acts as a donor. Propeller shaped triphenylamine has its effect on packing, processability and plays a vital role in determining the pi-pi molecular orbital stacking in such compounds and thus the mobility of charge carriers. With TDPPT and FDPPT, maximum hole carrier mobility obtained is 2.88?¡Á?10?3?cm2?V?1?s?1and 1.60?¡Á?10?3?cm2?V?1?s?1, respectively using bottom gate bottom contact field-effect transistor.

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

Brief introduction of 52409-22-0

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Recent advances in the synthesis of thioether

Organic thioether compounds had found extensive applications in the field of medicine, biology, agriculture, optical material and so on. The protocols synthesizing thioethers have always been an attractive interest to researchers. So far, various preparation methods involving diverse catalysts and promote reagents have been reported. A wide scope of newly published vital articles referring reactions of organic halides, alkenes, arenes, heteroaromatics and organic borides with sulfur source thiols, thiophenols, thioamides, potassium xanthate, potassium thiocyanate, elemental sulfur, sodium thiomethoxide, sodium sulfide, carbon disulphide, disulfides, sulfonyl hydrazides, AgSCF3, CuSCF3 with transition metal complexes catalyzation or with metal free method are comprehensively summarized in this review.

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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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Atom-transfer radical homo- and copolymerization of carbazole-substituted styrene and perfluorostyrene

Atom-transfer radical polymerization of 9-(4-vinylphenyl)carbazole (M1) and 9-(2,3,5,6-tetrafluoro-4-vinylphenyl)carbazole (M2) has been investigated using CuCl/N,N,N?,N??,N??-pentamethyldiethylenetriamine as catalyst and ethyl 2-bromoisobutyrate as an initiator. The polymerization of the monomers proceeded in a living fashion affording polymers with controlled molecular weight (Mn = 5000 g mol?1 to 32000 g mol?1) and relatively low polydispersity (? = 1.2?1.5). The kinetic investigations showed that M2 polymerized at the faster rate as compared to M1. Block copolymers were successfully prepared starting from the polymerization of more reactive M2 followed by addition of M1. The same initiating system also induced living radical copolymerization of these monomers giving random copolymers. Usage of tetrafunctional initiator pentaerythritol tetrakis(2-bromoisobutyrate) in conjunction with CuCl/N,N,N?,N??,N??-pentamethyldiethylenetriamine as catalyst allowed to synthesize star-shaped linear and random copolymers from M1 and M2 with controlled molecular weight (up to Mn = 25000 g mol?1) and low polydispersity (? < 1.5). The thermal, photophysical and electrochemical properties of the synthesized linear and star-shaped polymers and copolymers were estimated. It was shown that photophysical properties of copolymers can be tuned by changing the copolymer composition. Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Electric Literature of 52409-22-0. In my other articles, you can also check out more blogs about 52409-22-0

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

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Polyethylene as a nonvolatile solid cosolvent phase for catalyst separation and recovery

The studies described here show that a relatively low molecular weight, narrow polydispersity polyethylene (PE) wax (Polywax) can serve as a nontoxic and nonvolatile alternative to alkane solvents in monophasic catalytic organic reactions where catalysts and products are separated under biphasic conditions. In this application, a polymer that is a solid at room temperature substitutes for a conventional alkane solvent at ca. 80 C. In addition to the advantages of being a nonvolatile, nontoxic, reusable solvent, this hydrocarbon polymer solvent, like heptane, can sequester nonpolar soluble polymer-bound catalysts after a reaction and separate them from products. The extent of this separation and its generality were studied using polyisobutylene (PIB)- and poly(4-dodecylstyrene)-bound dyes and PE-bound Pd allylic substitution catalysts, PIB-bound Pd cross-coupling catalysts, and PE- and PIB-bound metathesis catalysts. Catalytic reactions were effected using single-phase reaction mixtures containing Polywax with toluene, THF, or THF/DMF at ca. 80 C. These solutions either separate into two liquid phases on addition of a perturbing agent or separate as a solid/liquid mixture on cooling. The hydrocarbon polymer-bound dyes or catalysts either separate into the hot liquid Polywax phase or coprecipitate with Polywax and are subsequently isolated as a nonvolatile Polywax solid phase that contains the dye or the recyclable catalyst.

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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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Mechanistic investigation of the bypass of a bulky aromatic DNA adduct catalyzed by a Y-family DNA polymerase

3-Nitrobenzanthrone (3-NBA), a nitropolyaromatic hydrocarbon (NitroPAH) pollutant in diesel exhaust, is a potent mutagen and carcinogen. After metabolic activation, the primary metabolites of 3-NBA react with DNA to form dG and dA adducts. One of the three major adducts identified is N-(2′-deoxyguanosin-8-yl)-3-aminobenzanthrone (dGC8-N-ABA). This bulky adduct likely stalls replicative DNA polymerases but can be traversed by lesion bypass polymerases in vivo. Here, we employed running start assays to show that a site-specifically placed dGC8-N-ABA is bypassed in vitro by Sulfolobus solfataricus DNA polymerase IV (Dpo4), a model Y-family DNA polymerase. However, the nucleotide incorporation rate of Dpo4 was significantly reduced opposite both the lesion and the template position immediately downstream from the lesion site, leading to two strong pause sites. To investigate the kinetic effect of dGC8-N-ABA on polymerization, we utilized pre-steady-state kinetic methods to determine the kinetic parameters for individual nucleotide incorporations upstream, opposite, and downstream from the dGC8-N-ABA lesion. Relative to the replication of the corresponding undamaged DNA template, both nucleotide incorporation efficiency and fidelity of Dpo4 were considerably decreased during dGC8-N-ABA lesion bypass and the subsequent extension step. The lower nucleotide incorporation efficiency caused by the lesion is a result of a significantly reduced dNTP incorporation rate constant and modestly weaker dNTP binding affinity. At both pause sites, nucleotide incorporation followed biphasic kinetics with a fast and a slow phase and their rates varied with nucleotide concentration. In contrast, only the fast phase was observed with undamaged DNA. A kinetic mechanism was proposed for the bypass of dGC8-N-ABA bypass catalyzed by Dpo4.

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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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Palladium-Catalyzed Reactions of Allylic Boronic Esters with Nucleophiles: Novel Umpolung Reactivity

Oxidative palladium-catalyzed reaction conditions have been developed to allow for regioselective and stereoselective coupling of allylic boronic esters with a range of carbon-, oxygen-, and nitrogen-based nucleophiles. Studies into the mechanism of the reaction have shown that the key transmetalation step occurs with retention of stereochemistry, since overall inversion is observed.

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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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N,N?-bisaryl substituted chiral linker-bridged bis(N-heterocyclic carbene) palladium complexes: Design, synthesis, and catalytic properties

A series of novel N,N?-bisaryl bis(NHC) (NHC = N-heterocyclic carbene) precursors 5a-e, 12a-d, and 13a-c and their palladium complexes 14a-e, 15a-d, and 16a,b with (1R,2R)-cyclohexene and (1R,2R)-diphenylethylene linkers have been designed, synthesized in good yields, and fully characterized by NMR, HRMS, and elemental analysis. The X-ray single crystal analysis of 15a showed that these complexes adopted a slightly distorted square-planar geometry around the Pd(II) center. These N,N?-bisaryl-bis(NHC)-Pd complexes exhibit excellent catalytic activity in asymmetric aryl.aryl cross-coupling reactions of arylboronic acids and aryl halides. The axial chiral biaryl compounds could be achieved in high yields (up to 74%) and good enantioselectivities (up to 60% ee) within 24 h. The results show that for this kind of bis(NHC) palladium catalysts the structure characteristics of the chiral linkers have decisive effect on the enantioselectivities of cross-coupling reactions.

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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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Deposition of palladium nanoparticles in SBA-15 templated silica using supercritical carbon dioxide

Preparation of supported nanoparticles by palladium deposition onto silica (SBA-15) from a solution of tris(dibenzylideneacetone) dipalladium(0) (Pd 2(dba)3) in supercritical carbon dioxide (scCO 2) was successfully achieved. Pd2(dba)3 avoided agglomeration of nanoparticles, which is typically associated with secondary processes including reduction of metal salts. scCO2 impregnation was superior at depositing palladium nanoparticles within the porous channels of SBA-15, as compared to organic solvents. The resulting material demonstrated significant potential for use in catalytic applications including hydrogenations and showed specific selectivity towards alkene hydrogenation.

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