4.4. Pd on Modified Silica 159 4.5. Pd on Clay and Other Inorganic Materials 159 5. Stille, Fukuyama, and Negishi Reactions 159 5.1. Stille Reactions 159 5.1.1. Pd on Carbon (Pd/C) 159 5.1.2. Palladium on KF/Al2O3 159 5.1.3. Pd on Modified Silica (SiO2/TEG/Pd) 159 5.2. Fukuyama Reactions 159 5.2.1. Pd on Carbon (Pd/C) 159 5.2.2. Pd(OH)2 on Carbon (Perlman’s Catalyst) 160 5.3. Pd/C-Catalyzed Negishi Reactions 160 6. Ullmann-Type Coupling Reactions 161 6.1. Pd/C-Catalyzed Aryl−Aryl Coupling 161 6.2. Pd/C-Catalyzed Homocoupling of Vinyl Halides 162

https://www.chem.ccu.edu.tw/~joyce/referance/ericyang/Chem.%20Rev/Chem.%20Rev.%202007,%20107,%20133-173.pdf

Carbon-Carbon Coupling Reactions Catalyzed by Heterogeneous Palladium Catalysts

A wide array of forms of palladium has been utilized as precatalysts for Heck and Suzuki coupling reactions over the last 15 years. Historically, nearly every form of palladium used has been described as the active catalytic species. However, recent research has begun to shed light on the in situ transformations that many palladium precatalysts undergo during and before the catalytic reaction, and there are now many suggestions in the literature that narrow the scope of types of palladium that may be considered true “catalysts” in these coupling reactions. In this work, for each type of precatalyst, the recent literature is summarized and the type(s) of palladium that are proposed to be truly active are enumerated. All forms of palladium, including discrete soluble palladium complexes, solid-supported metal ligand complexes, supported palladium nano- and macroparticles, soluble palladium nanoparticles, soluble ligand-free palladium, and palladium-exchanged oxides are considered and reviewed here. A considerable focus is placed on solid precatalysts and on evidence for and against catalysis by solid surfaces vs. soluble species when starting with various precatalysts. The review closes with a critical overview of various control experiments or tests that have been used by authors to assess the homogeneity or heterogeneity of catalyst systems.

On the Nature of the Active Species in Palladium Catalyzed Mizoroki–Heck and Suzuki–Miyaura Couplings – Homogeneous or Heterogeneous Catalysis, A Critical Review

Transition-Metal-Catalyzed C−S, C−Se, and C−Te Bond Formation via Cross-Coupling and Atom-Economic Addition Reactions

The coupling of aryl or vinyl halides with terminal acetylenes catalysed by palladium and other transition metals, commonly termed as Sonogashira cross-coupling reaction, is one of the most important and widely used sp2–sp carbon–carbon bond formation reactions in organic synthesis, frequently employed in the synthesis of natural products, biologically active molecules, heterocycles, molecular electronics, dendrimers and conjugated polymers or nanostructures. This critical review focuses on developments in the Sonogashira reaction achieved in recent years concerning catalysts, reaction conditions and substrates (352 references).

Recent advances in Sonogashira reactions

Palladium-catalyzed carbonylation reactions of aromatic halides in the presence of various nucleophiles have undergone rapid development since the pioneering work of Heck and co-workers in 1974, such that nowadays a plethora of palladium catalysts are available for different carbonylative transformations. The carboxylic acid derivatives, aldehydes, and ketones prepared in this way are important intermediates in the manufacture of dyes, pharmaceuticals, agrochemicals, and other industrial products. In this Review, the recent academic developments in this area and the first industrial processes are summarized.

Palladium-catalyzed carbonylation reactions of aryl halides and related compounds.

Heterogeneous Copper‐Catalyzed Cascade Three‐Component Reaction Towards Imidazo[1,2‐a]pyridines: Efficient and Practical One‐Pot Synthesis of Alpidem

A silica-supported poly-ω-(methylseleno)undecylsiloxane palladium(0) complex has been prepared from ω-chloroundecyltriethoxysilane via immobilization on fumed silica, followed by reacting with sodium methylselenolate in ethanol and palladium chloride in acetone and then the reduction with hydrazine hydrate in ethanol. The complex is a highly active and stereoselective catalyst for arylation of conjugated alkenes with aryl halides. This polymeric palladium catalyst can be recovered and reused.

Synthesis of silica-supported poly-ω-(methylseleno)undecylsiloxane palladium(0) complex and its catalytic properties for Heck arylation of alkenes

New monomers, 4,4′-bis(4-phenoxybenzoyl)diphenyl (BPOBDP) and N,N′-bis(4-phenoxybenzoyl)−4,4′-diaminodiphenyl ether (BPBDAE), were conveniently synthesized via simple synthetic procedures from readily available materials Novel copolymers of poly(ether ketone diphenyl ketone ether ketone ketone) (PEKDKEKK) and poly(ether amide ether amide ether ketone ketone) (PEAEAEKK) were synthesized by electrophilic Friedel-Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of BPOBDP and BPBDAE, over a wide range of BPOBDP/BPBDAE molar ratios, in the presence of anhydrous AlCl3 and N-methylpyrrolidone (NMP) in 1,2-dichloroethane (DCE) The copolymers obtained were characterized by different physico-chemical techniques The copolymers with 10–40 mol% BPBDAE are semicrystalline and had remarkably increased Tgs over commercially available PEEK and PEKK due to the incorporation of amide and diphenyl linkages in the main chains The copolymers IV and V with 30–40 mol% BPBDAE had not only high Tgs of 185–188°C, but also moderate Tms of 326–330°C, having good potential for the melt processing The copolymers IV and V had tensile strengths of 1017–1023 MPa, Young's moduli of 219–242 GPa, and elongations at break of 132–166% and exhibited high thermal stability and excellent resistance to organic solvents POLYM ENG SCI, 54:1757–1764, 2014 © 2013 Society of Plastics Engineers

Synthesis and properties of novel copolymers of poly(ether ketone diphenyl ketone ether ketone ketone) and poly(ether amide ether amide ether ketone ketone)

A highly efficient heterogeneous ruthenium(III)-catalyzed reaction of diaryl diselenides with alkyl halides leading to unsymmetrical diorganyl selenides

Mingzhong Cai

Papers

Heterogeneous Copper‐Catalyzed Cascade Three‐Component Reaction Towards Imidazo[1,2‐a]pyridines: Efficient and Practical One‐Pot Synthesis of Alpidem

Synthesis of silica-supported poly-ω-(methylseleno)undecylsiloxane palladium(0) complex and its catalytic properties for Heck arylation of alkenes

Synthesis and properties of novel copolymers of poly(ether ketone diphenyl ketone ether ketone ketone) and poly(ether amide ether amide ether ketone ketone)

A highly efficient heterogeneous ruthenium(III)-catalyzed reaction of diaryl diselenides with alkyl halides leading to unsymmetrical diorganyl selenides

Heterogeneous copper-catalyzed three-component reaction of 2-aminopyridines, acetophenones and benzyl cyanide towards 3-cyanoimidazo[1,2-a]pyridines