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Palladium-catalyzed dearomative trimethylenemethane cycloaddition reactions

A general protocol for the palladium-catalyzed dearomative trimethylenemethane [3+2] cycloaddition reaction with simple nitroarene substrates is described. This methodology leads to the exclusive formation of the dearomatized alicyclic products without subsequent rearomatization. The reaction is tolerant toward a broad range of heterocyclic and benzenoid substrates. The use of chiral bisdiamidophosphite ligands enabled the development of an enantioselective variant of this transformation, representing one of the rare examples of an asymmetric catalytic dearomatization process.

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

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Palladium-Catalyzed Arylation of Aryl Sulfenate Anions with Aryl Bromides under Mild Conditions: Synthesis of Diaryl Sulfoxides

A palladium-catalyzed arylation of aryl sulfenate anions generated from aryl 2-(trimethylsilyl)ethyl sulfoxides and CsF has been developed. This protocol is effective for the synthesis of diaryl sulfoxides and heteroaryl aryl sulfoxides under mild conditions employing aryl bromides. Various functional groups, including those with acidic protons, are well tolerated.

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

Simple exploration of Bis(dibenzylideneacetone)palladium

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Pd-catalyzed dearomative arylborylation of indoles

A palladium-catalyzed dearomative arylborylation of indoles is reported, which provides straightforward access to structurally diverse indolines bearing vicinal tetrasubstituted and borylated trisubstituted stereocenters in moderate to good yields with excellent diastereoselectivities. By using a BINOL-based chiral phosphoramidite ligand and an sp2-sp3 mixed-boron reagent, an enantioselective dearomative arylborylation was achieved and chiral boron-containing products were accessed in up to 94% ee. Synthetic tranformations of the resulting organoborons were conducted to afford a number of unique indoline derivatives.

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

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Supramolecular Structure-Dependent Thermally-Activated Delayed Fluorescence (TADF) Properties of Organic Polymorphs

The increasing demand for high-performance organic light-emitting devices (OLEDs) based on thermally-activated delayed fluorescence (TADF) principle urgently requires to establish an efficient preparation strategy of high-performance TADF materials. Although considerable progress has been made in molecular design approaches for TADF materials, it still remains an unaddressed issue how molecular aggregated states or supramolecular structures determine the TADF property of organic solids. Herein, we present an organic molecule 3-(10H-phenoxazin-10-yl)-9H-xanthen-9-one (3-PXZ-XO) with TADF and polymorph characteristics. Three kinds of 3-PXZ-XO based crystals A, B, and C with different TADF properties were obtained. The three crystals display obviously different emission maxima (lambdaem,max: 535 nm for A, 555 nm for B, and 576 nm for C), photoluminescence (PL) quantum yields (phi: 51% for A, 28% for B, and 39% for C), and delayed lifetimes of excited states (tauTADF: 914 ns for A, 774 ns for B, and 994 ns for C). Single-crystal X-ray diffraction analyses revealed that in A, B, and C there are different intermolecular pi···pi stacking interaction modes between the adjacent donor planes or acceptor planes. The different TADF properties of the three polymorphs are mainly attributed to their different supramolecular structures. Appropriate donor···donor and acceptor···acceptor stacking interactions inducing aggregation structures can strongly enhance TADF property of organic solids.

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

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Intramolecularly stabilised group 10 metal stannyl and stannylene complexes: Multi-pathway synthesis and observation of platinum-to-tin alkyl transfer

Reaction of [PdClMe(P?N)2] with SnCl2 followed by Cl-abstraction leads to apparent Pd-C bond activation, resulting in methylstannylene species trans-[PdCl{(P?N)2SnClMe}][BF4] (P?N = diaryl phosphino-N-heterocycle). In contrast, reaction of Pt analogues with SnCl2 leads to Pt-Cl bond activation, resulting in methylplatinum species trans-[PtMe{(P?N)2SnCl2}][BF4]. Over time, they isomerise to methylstannylene species, indicating that both kinetic and thermodynamic products can be isolated for Pt, whereas for Pd only methylstannylene complexes are isolated. Oxidative addition of RSnCl3 (R = Me, Bu, Ph) to M0 precursors (M = Pd or Pt) in the presence of P?N ligands results in diphosphinostannylene pincer complexes trans-[MCl{(P?N)2SnCl(R)}][SnCl4R], which are structurally similar to the products from SnCl2 insertion. This showed that addition of RSnCl3 to M0 results in formal Sn-Cl bond oxidative addition. A probable pathway of activation of the tin reagents and formation of different products is proposed and the relevancy of the findings for Pd and Pt catalysed processes that use SnCl2 as a co-catalyst is discussed.

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

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Palladium-catalyzed asymmetric allylic alkylation of acyclic ketones for synthesis of 2,2-disubsituted pyrrolidine derivatives

Palladium-catalyzed asymmetric allylic alkylation of acyclic ketones represents a significant challenge in organic synthesis. We report herein that the synthesis of chiral 2,2-disubsituted pyrrolidines from acyclic ketones has been accomplished by using catalytic asymmetric method in the presence of Pd(dba)2 and (R)-binap ligand. Theses reactions occur between allyl methyl carbonate and unstabilized acyclic lithium enolates to provide the products in moderate to good enantioselectivity (up to 81% ee).

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

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Catalyst system

The present invention provides a catalyst system capable of catalyzing the carbonylation of an ethylenically unsaturated compound, which system is obtainable by combining: a) a metal of Group VIB or Group VIIIB or a compound thereof, b) a bidentate phosphine, arsine or stibine ligand, and c) an acid, wherein the ligand is present in at least a 2:1 molar excess compared to the metal or the metal in the metal compound, and that the acid is present in at least a 2:1 molar excess compared to the ligand, a process for the carbonylation of an ethylenically unsaturated compound, a reaction medium, and use of the system.

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

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Direct cross-coupling access to diverse aromatic sulfide: Palladium-catalyzed double C-S bond construction using Na2S 2O3 as a sulfurating reagent

The Pd-catalyzed cross-coupling of aryl halides, alkyl halides, and Na 2S2O3·5H2O to deliver aromatic thioethers is described. Pyridine, furan, thiophene, benzofuran, benzoxazole, benzothiophene, benzothiazole, and pyrazine are all amenable to this protocol. The odorless and stable solid Na2S2O 3·5H2O was used as a convenient and environmentally friendly source of sulfur. Pd-catalyzed cross-couplings without thiols or thiophenols to build C-S bonds have not previously been achieved, which renders our observation more striking.

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

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Synthetic and structural studies on the transition-metal fullerene complexes (eta2-C60)M[(eta5-Ph 2PC5H4)2Ru]

A toluene solution of C60 reacted with an equimolar quantity of M(dba)2 (M = Pd, Pt; dba = dibenzylideneacetone) and (eta 5-Ph2PC5H4)2Ru or with M(PPh3)4 and (eta5Pb2PC 5H4)2Ru at room temperature to give the dinuclear transition-metal fullerene complexes (eta2-C 60)M[(eta5Ph2PC5H 4)2Ru] (1, M = Pd; 2, M = Pt), whereas the o-dichlorobenzene solution of C60 reacted with an equimolar amount of M(dba)2 and [(eta5-Ph2PC5H 4)2Co]+(PF6)- or with M(PPh3)4 and [(eta5-Ph2PC 5H4)2Co]+(PF6) – under similar conditions to afford the dinuclear transition-metal fullerene complexes (eta2-C60)M[(eta 5-Ph2PC5H4)2Co] +(PF6)- (3, M = Pd; 4, M = Pt). In addition, the related complex {[eta5-Ph2P(O)C6H 4]2Co}+(PF6)- (5) was prepared by oxidation of [(eta5-Ph2-PC5H 4)2Co]+(PF6)- with an excess amount of aqueous peracetic acid in acetone at room temperature. While 1-4 are the first examples of neutral and cationic dinuclear M/Ru and M/Co (M = Pd, Pt) fullerene complexes, 5 is the first organocobalt Cp complex containing a phosphoryl substituent. All products 1-5 have been fully characterized by elemental analysis, spectroscopy, and X-ray crystal diffraction techniques and, for 1 and 2, by cyclic voltammetry.

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

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Arylation of Adamantanamines: X. Palladium- and Copper-Catalyzed Heteroarylation of Adamantane-Containing Amines with Bromopyridines

The catalytic efficiencies of palladium(0) and copper(I) complexes in the amination of 2-bromopyridine and its fluorine-containing derivatives with (1-adamantyl)methanamine and 2-(1-adamantyloxy)ethanamine were compared. Both types of catalytic systems were shown to be applicable for the preparation of the corresponding N-pyridyl derivatives from 3- and 5-fluoro- and 4-, 5-, and 6-trifluoromethyl-2-bromopyridines. DavePhos was found to be the most efficient ligand in the Pd(0)-catalyzed reactions; however, the reactions with 2-bromo-4-(trifluoromethyl)pyridine and 2-bromo-5-(trifluoromethyl)pyridine were accompanied by formation of a considerable amount of the diarylation product. The diarylation process was significantly suppressed in the presence of copper(I) complexes.

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