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.

Hydromagnesiation of alkynylsilanes 1 gives (Z)-α-silylvinyl Grignard reagents 2, which are reacted with alkyl iodides or aryl iodides in the presence of Cul or Pd(PPh 3 ) 4 catalysts to afford (Z)-1,2-disubstituted vinylsilanes 3 in good yields. Intermediates 3 can undergo a desilylation reaction to give (E)-disubstituted alkenes 4 in high yields.

Alkynylsilanes as Convenient Precursors for the Stereoselective Synthesis of (E)-Disubstituted Alkenes.

The first phosphane-free, heterogeneous, atom-efficient cross-coupling reaction of triarylbismuths and acyl chlorides was achieved in N-methylpyrrolidone (NMP) with Bu3N as the base at 80 °C in the presence of 1.5 mol-% MCM-41-immobilized bidentate nitrogen palladium complex [MCM-41–2N-Pd(OAc)2, MCM = mobile crystalline material] to yield a variety of unsymmetrical biaryl ketones in good to excellent yields. This heterogeneous palladium catalyst exhibited a high activity, which was similar to that of Pd(PPh3)4. The catalyst can be recovered by a simple filtration of the reaction solution and recycled in at least 10 consecutive trials without any decrease in activity. Our system not only avoids the use of phosphane ligands, but also solves the basic problem of palladium catalyst recovery and reuse.

A Phosphane-Free, Atom-Efficient Cross-Coupling Reaction of Triarylbismuths with Acyl Chlorides Catalyzed by MCM-41-Immobilized Palladium Complex.

Title compounds (V) may undergo further functionalization as is demonstrated in the synthesis of Stille coupling product (VII).

Stereoselective Synthesis of Difunctionalized 1,3‐Dienes Containing Tin and Sulfonyl Groups by Palladium‐Catalyzed Regio‐ and Stereocontrolled Addition Reactions.

A heterogeneous Chan–Lam coupling reaction between sulfonyl azides and arylboronic acids was achieved in MeOH at room temperature in the presence of 10 mol% of an L-proline-functionalized MCM-41-immobilized copper(I) complex [MCM-41–L-proline–CuCl] under air, yielding a variety of N-arylsulfonamides in excellent yields. The new heterogeneous copper complex can be prepared from commercially readily available and inexpensive reagents, and recovered by simple filtration of the reaction solution and recycled at least 8 times without any decreases in activity.

Mingzhong Cai

Papers

Alkynylsilanes as Convenient Precursors for the Stereoselective Synthesis of (E)-Disubstituted Alkenes.

A Phosphane-Free, Atom-Efficient Cross-Coupling Reaction of Triarylbismuths with Acyl Chlorides Catalyzed by MCM-41-Immobilized Palladium Complex.

Stereoselective Synthesis of Difunctionalized 1,3‐Dienes Containing Tin and Sulfonyl Groups by Palladium‐Catalyzed Regio‐ and Stereocontrolled Addition Reactions.

A Highly Efficient Heterogeneous Copper-Catalyzed Chan-Lam Coupling Reaction of Sulfonyl Azides with Arylboronic Acids Leading to N-Arylsulfonamides.

A Facile Stereoselective Synthesis of 1,3-Dienyltellurides via Palladium Catalyzed Cross-Coupling Reactions.