Summary of common metal-catalyzed reactions
Metal-catalyzed coupling reactions are common in organic synthesis for the formation of carbon-carbon and carbon-heterobonds, and have a crucial role in organic synthesis.
I. Palladium-catalyzed reactions
1、Suzuki-Miyaura reaction
Suzuki reaction (Suzuki reaction), also known as Suzuki coupling reaction, Suzuki-Miyaura reaction (Suzuki-Miyaura reaction), is a relatively new organic coupling reaction, zero-valent palladium complex-catalyzed, aryl or alkenyl boronic acid or boronic ester and chlorine, bromine, iodine-substituted aromatic hydrocarbons or olefins to occur in the cross-coupling. This reaction was first reported by Akira Suzuki in 1979, and has been widely used in organic synthesis with strong substrate adaptability and functional group tolerance, and is commonly used in the synthesis of polyolefins, styrene and biphenyl derivatives, which have been applied to the synthesis of many natural products and organic materials. Shoji Suzuki was awarded the 2010 Nobel Prize in Chemistry together with Richard Heck and Eiichi Negishi for his contributions.
Example of Suzuki reaction involving 9-BBN
Suzuki reaction catalyzed by palladium catalysts with phosphine-free ligands
Suzuki coupling reaction catalyzed by aryl chloride
Examples of Suzuki coupling reactions involving potassium alkylfluoroborate
2. Miyaura borate esterification reaction
Palladium-catalyzed reaction of aryl halides and bis-boron reagents to prepare aryl borate esters. It is also called Hosomi-Miyaura boronation reaction.
Preparation of monosubstituted arylboronic acids by metal-organic reagents
Examples of the preparation of organoboronic acids and their derivatives
3、Buchwald-Hartwig reaction
The Buchwald-Hartwig aryl amination reaction is a very common reaction for the preparation of aryl amines from aryl halogenates or aryl sulfonates. The main feature of this reaction is the use of catalytic amounts of palladium and electron-rich ligands to catalyze the reaction. In addition strong bases (e.g. sodium tert-butanol) are essential for the catalytic cycle.
Introduction to the Buchwald-Hartwig C-N coupling reaction
Common ligands in Buchwald-Hartwig coupling reactions
The 25th Anniversary of the Buchwald-Hartwig Coupling
4. Heck reaction
Palladium-catalyzed alkenylation or arylation of olefins. In addition, halogenated hydrocarbons that do not contain β-hydrogen (mainly benzyl halide) can also undergo alkylation by the Heck reaction.
[Encyclopedia of organic reactions] Narasaka-Heck cyclization reaction
5、Heck reaction of aromatic heterocycles
Aromatic heterocyclic ring as an acceptor occurs in the intramolecular or intermolecular Heck reaction.
6、Heck reaction involving diazonium saltImage
Aryl diazonium salts can be the most common reaction is the Sandmeyer reaction can be prepared halogenated aromatic hydrocarbons, aryl phenols or aryl nitrile, in addition to the Balz-Schiemann reaction for the preparation of aryl fluoride, azo coupling reaction for the preparation of azodiaromatic compounds, in 1995, Beller et al. reported that the use of diazonium salts as the substrate for the preparation of aryl alkenyls as a substrate in the Heck reaction, which is a very practical way to prepare aryl alkenyls. In 1995, Beller et al. reported the use of diazonium salts as substrates for the Heck reaction to prepare aryl alkenes, which is a very practical reaction for the preparation of aryl olefins, such reactions do not require phosphine catalysts and amines, and the conditions are mild.
7、Sonogashira reaction
Pd/Cu-catalyzed coupling of aryl halogen or alkenyl halogen substitutes and terminal alkynes. Reaction mechanism and Cadiot-Chodkiewicz coupling and Castro-Stephens reaction is similar. Castro-Stephens reaction is catalyzed by chemical equivalent of copper, while Sonogashira reaction is catalyzed by catalytic amount of palladium and copper.
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