This Review summarizes the advancements in Pd-catalyzed C(sp3)–H activation via various redox manifolds, including Pd(0)/Pd(II), Pd(II)/Pd(IV), and Pd(II)/Pd(0). While few examples have been reported in the activation of alkane C–H bonds, many C(sp3)–H activation/C–C and C–heteroatom bond forming reactions have been developed by the use of directing group strategies to control regioselectivity and build structural patterns for synthetic chemistry. A number of mono- and bidentate ligands have also proven to be effective for accelerating C(sp3)–H activation directed by weakly coordinating auxiliaries, which provides great opportunities to control reactivity and selectivity (including enantioselectivity) in Pd-catalyzed C–H functionalization reactions.

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Palladium-Catalyzed Transformations of Alkyl C-H Bonds.

Iron Catalysis in Organic Synthesis

Isatins As Privileged Molecules in Design and Synthesis of Spiro-Fused Cyclic Frameworks

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

140 years ago Adolf von Baeyer proposed the structure of a heteroaromatic compound which revolutionized organic and medical chemistry: indole. After more than a century, indole itself and the complexity of naturally occurring indole derivatives continue to inspire and influence developments in synthetic chemistry. In particular, the ubiquitous presence of indole rings in pharmaceuticals, agrochemicals, and functional materials are testament to the ever increasing interest in the design of mild and efficient synthetic routes to functionalized indole derivatives. This Review emphasizes the achievements in the selective catalytic functionalization of indoles (C-C bond-forming processes) over the last four years.

Catalytic Functionalization of Indoles in a New Dimension

An efficient one-pot synthesis of spirooxindole derivatives by three-component reaction of isatins, malononitrile (cyanoacetic ester) and 1,3-dicarbonyl compounds in water in the presence of l-proline is reported This new protocol has the advantages of environmental friendliness, higher yields, shorter reaction times, low cost, and convenient operation

Efficient one-pot synthesis of spirooxindole derivatives catalyzed by L-proline in aqueous medium.

One-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones using boric acid as catalyst

An efficient one-pot synthesis of spiro[indoline-3,4′-pyrano[2,3-c]pyrazole] derivatives by four-component reaction of hydrazine, β-keto ester, isatin, and malononitrile or ethyl cyanoacetate catalyzed by piperidine under ultrasound irradiation is described. This synthesis was confirmed to follow the group-assistant-purification chemistry (GAP) chemistry process, which can avoid traditional chromatography and recrystallization purifications.

Rapid and efficient ultrasound-assisted method for the combinatorial synthesis of spiro[indoline-3,4'-pyrano[2,3-c]pyrazole] derivatives.

A Convenient Synthesis of 5-Oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran Derivatives Catalyzed by KF-Alumina

A novel and efficient one-pot synthesis of spiro[indoline-3,4′-pyrazolo[3,4-b]quinoline]dione, spiro[furo[3,4-e]pyrazolo[3,4-b]pyridine-4,3′-indoline]dione, and spiro[indeno[2,1-e]pyrazolo[3,4-b]pyridine-4,3′-indoline]dione derivatives via three-component reaction of isatin, 5-amino-3-methylpyrazole, and 1,3-dicarbonyl compounds in aqueous medium is described. The advantages of this method include high efficiency, mild reaction conditions, convenient operation, and environmentally benign conditions.

Daqing Shi

Papers

Efficient one-pot synthesis of spirooxindole derivatives catalyzed by L-proline in aqueous medium.

One-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones using boric acid as catalyst

Rapid and efficient ultrasound-assisted method for the combinatorial synthesis of spiro[indoline-3,4'-pyrano[2,3-c]pyrazole] derivatives.

A Convenient Synthesis of 5-Oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran Derivatives Catalyzed by KF-Alumina

Efficient One-Pot Synthesis of Novel Spirooxindole Derivatives via Three-Component Reaction in Aqueous Medium