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Selective formation of alpha,omega-ester amides from the aminocarbonylation of castor oil derived methyl 10-undecenoate and other unsaturated substrates

The reaction of long chain alkenes with CO and aniline in the presence of palladium complexes of 1,2-bis-(ditertbutylphosphinomethyl)benzene produces amides with high linear selectivity, with much higher rates and catalyst stability when 2-naphthol and sodium or potassium iodide are added. Unsaturated esters including methyl 10-undecenoate from castor oil give alpha,omega- ester amides, whilst reactions in THF give N-phenylpyrrolidine.

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

The important role of Pd2(DBA)3

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Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of N-Mesylamides by N-C Cleavage: Electronic Effect of the Mesyl Group

A general Pd-catalyzed Suzuki-Miyaura cross-coupling of N-mesylamides with arylboronic acids by selective N-C cleavage has been developed. The presented results represent the first example of a transition-metal-catalyzed cross-coupling of amides activated by an atom-economic, cheap, and benign mesyl group. The reaction delivers arylated products featuring a range of useful functional groups by chemoselective cleavage of the amide N-C bond with high efficiency. Both the scope and the origin of high selectivity are discussed. A beneficial effect of the N-mesyl substituent on the bond activation in acyclic amides is presented.

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

Properties and Exciting Facts About 52409-22-0

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Synthesis of axially chiral 1,1?-binaphthalenes by palladium-catalysed cross-coupling reactions of triorganoindium reagents

1,1?-Binaphthalenes and heterocyclic analogues can be efficiently prepared by palladium-catalysed cross-coupling reactions between tri(1-naphthyl)indium reagents and 1-halonaphthalenes and haloisoquinolines. The reactions were usually carried out in THF at 80 C with a slight excess of the indium reagent (40 mol-%) and a low catalyst loading (4 mol-% Pd) to afford the cross-coupling products in good yields (45-99 %). The method allows the synthesis of sterically hindered 2-substituted and 2,2?-disubstituted 1,1?-binaphthalenes and naphthylisoquinolines. In addition, the coupling reactions can be performed enantioselectively and the best enantiomeric excesses were obtained by using the chiral amino-phosphane ferrocenyl ligand (R,S)-PPFA. 1,1?-Binaphthalenes and heterocyclic derivatives have been synthesized by palladium-catalysed cross-coupling reactions between tri(1-naphthyl)indium reagents and 1-halonaphthalenes and haloisoquinolines, including 2-substituted and 2,2?-disubstituted 1,1?-binaphthyls. The coupling reactions can be performed enantioselectively in the presence of the chiral ligand (R,S)-PPFA. Copyright

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

Final Thoughts on Chemistry for Pd2(DBA)3

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Pd(0)-catalyzed cross-coupling of allyl halides with alpha-diazocarbonyl compounds or N-mesylhydrazones: Synthesis of 1,3-diene compounds

With palladium catalysis, allyl bromides or chlorides react with alpha-diazocarbonyl compounds or N-mesylhydrazones to afford 1,3-diene derivatives. The reaction represents a novel and efficient method for the synthesis of 1,3-butadiene derivatives. Mechanistically, the reaction is proposed to follow a pathway involving the formation of a pi-allylic palladium carbene complex and subsequent migratory insertion.

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

Properties and Exciting Facts About Pd2(DBA)3

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Potential Safety Hazards Associated with Pd-Catalyzed Cross-Coupling Reactions

The potential safety hazards associated with Pd-catalyzed cross-coupling reactions have been underappreciated and inadequately discussed. These hazards have not been universally recognized in the past decades, perhaps overshadowed by the ubiquity of this class of chemistry and the desire to pursue new scientific advancements. The awareness of these hazards is further limited by the fact that synthetic chemists who develop these types of reactions on small scales are not typically trained in reactive chemistry hazard evaluation, and existing studies from industrial chemists and chemical engineers are often not published in journals that are commonly read by academic groups and synthetic chemists that typically work on small scales. This review summarizes observations of the exothermic behavior associated with the Pd-catalyzed alpha-arylation, Buchwald-Hartwig amination, Kumada-Corriu, Mizoroki-Heck, Negishi, Sonogashira, and Suzuki-Miyaura cross-coupling reactions. This exothermic behavior is consistently observed across each subset of cross-coupling reactions and appears to be relatively independent of the nucleophile, electrophile, base, solvent, and catalyst system employed. The magnitude of the exotherms poses potential safety hazards that could result in runaway scenarios in cases where the maximum temperature of a synthesis reaction (MTSR) exceeds the solvent boiling point and/or the onset temperature for reaction mixture decomposition. This contribution will serve as an educational resource to encourage researchers to conduct reaction safety evaluations and to develop control strategies accordingly to mitigate such potential safety risks prior to practicing Pd-catalyzed cross-coupling as well as other transition-metal-catalyzed cross-coupling reactions.

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

Archives for Chemistry Experiments of Pd2(DBA)3

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Syntheses of donor-acceptor-functionalized dihydroazulenes

The dihydroazulene (DHA)/vinylheptafulvene (VHF) photo/thermoswitch has been of interest for use in molecular electronics and advanced materials. The switching between the two isomers has previously been found to depend strongly on the presence of donor and acceptor groups. The fine-tuning of optical and switching properties relies on ready access to new derivatives via efficient synthetic protocols. The central DHA core is conveniently prepared in a four-step synthesis starting from acetophenone and tropylium substrates. Here, the outcome of this reaction as a function of the nature of the substituent group on the phenyl unit of acetophenone is investigated in detail. A wide variety of functional groups (nitro, cyano, halo, alkyl, amido, and thioether) was tolerated, and the route provided access to a large selection of substituted DHA derivatives (position 2 of DHA). These compounds were investigated for their ability to undergo subsequent functionalization in the seven-membered ring by a regioselective bromination-elimination protocol, introducing a bromo substituent at position 7. Halo-substituted DHAs were subjected to palladium-catalyzed cyanation, Sonogashira, Cadiot-Chodkiewicz, and Suzuki couplings and for the latter reaction; optimized conditions were developed by varying the palladium catalyst. In general, our focus was on reducing the formation of fully unsaturated azulene byproducts.

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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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Copper- versus palladium-catalyzed aromatization of 2-(methoxycarbonyl) tetralones: Synthesis of methyl 1-hydroxy-2-naphthoates

The aromatization of alpha-tetralones substituted at the beta-position by an ester group is reported using either CuI or Pd2(dba)3. In the case of using CuI (10 mol %) as catalyst and Cs2CO3 as base in dioxane, 2-(methoxycarbonyl)-alpha-tetralones are smoothly converted into the corresponding methyl 1-hydroxy-2-naphthoates at 70 C under air. Alternatively, Pd2(dba)3 (1.25 mol %) can also be used as catalyst in the presence of K3PO4 as base in toluene also at 70 C under argon. These are the most straightforward methodologies for the aromatization of these types of alpha-tetralones. CuI is the catalyst of choice due to higher efficiency, economical and practical reasons.

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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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Progress towards the Total Syntheses of Lycopodium Alkaloid, Lycopladine A

Several alkaloids derived from discrete Lycopodium species can treat Alzheimer’s disease and increase the efficiency of learning and memory in animals. Thus, Lycopodium alkaloids bearing amazingly unique hetero-polycyclic ring scaffolds persuaded scientists to look upon its biogenetic and biosynthetic pathways and to design its ambitious total syntheses. Recently, a C16N type Lycopodium alkaloid, (+)-lycopladine A; isolated from the club moss Lycopodium complanatum, showed selective but modest cytotoxicity towards murine lymphoma L1210 cells (IC50 7 mug/mL). Owing to its dense array of stereochemical features, as well as intriguing biological activity, lycopladine A has been an important synthetic target for last 12 years. An overview of the synthetic studies of lycopladine A is presented, covering literature from 2006 until March 2019.

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

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Pd0-Catalyzed Four-Component Reaction of Aryl Halide, CO, N-Tosylhydrazone, and Amine

A Pd0-catalyzed four-component cascade reaction of an aryl halide, CO, an N-tosylhydrazone, and an amine affording alpha-amino ketone has been developed. This reaction involves a sequential carbonylation, metal carbene migratory insertion, and amination. Control experiments and DFT calculations further reveal the reaction sequence and chemoselectivity of individual components in this cascade process.

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

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Comprehension of the alpha-arylation of nitroalkanes

Background: alpha-Aryl substituted nitroalkanes are important synthetic intermediates for the preparation of pharmaceutical molecules, natural products, and functional materials. Due to their scare existence in Nature, synthesis of these compounds has attracted the attention of synthetic and medicinal chemists, rendering alpha-arylation of nitroalkanes of an important research topic. This article summarizes the important advances of alpha-arylation of nitroalkanes since 1963. Results: After a brief introduction of the synthetic application and the reactions of nitroalkanes, this article reviewed the synthetic methods for the alpha-arylated aliphatic nitro compound. The amount of research on alpha-arylation of nitroalkanes using various arylation reagents and the discovery of elegant synthetic approaches towards such skeleton have been discussed. This review described these advances in two sections. One is the arylation of non-activated nitroalkanes, with an emphasis on the application of diverse arylation reagents; the other focuses on the arylation of activated nitroalkanes, including dinitroalkanes, trinitroalkanes, alpha-nitrosulfones, alpha-nitroesters, alpha-nitrotoluenes, and alpha-nitroketones. The synthetic application of these methods has also been presented in some cases. Conclusion: In this review, we described the progress of alpha-arylation of nitroalkanes. Although the immense amount of research on alpha-arylation of aliphatic nitro compounds has been achieved, many potential issues still need to be addressed, especially the asymmetric transformation and its wide application in organic synthesis.

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