Discovery and Understanding of Transition-Metal-Catalyzed Aromatic Substitution Reactions

ChemInform ◽  
2006 ◽  
Vol 37 (37) ◽  
Author(s):  
John F. Hartwig
Keyword(s):  
Transition Metal ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

Transition-Metal-Catalyzed Synthesis of Organophosphorus Compounds Involving P–P Bond Cleavage

Synthesis ◽  
2020 ◽  
Vol 52 (19) ◽  
pp. 2795-2806 ◽  
Author(s):  
Mieko Arisawa
Keyword(s):  
Transition Metal ◽  
Organophosphorus Compounds ◽  
Bond Cleavage ◽  
Palladium Complexes ◽  
Addition Reactions ◽  
Phosphonium Salts ◽  
Substitution Reactions ◽  
Sulfonic Acids ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

Organophosphorus compounds are used as drugs, pesticides, detergents, food additives, flame retardants, synthetic reagents, and catalysts, and their efficient synthesis is an important task in organic synthesis. To synthesize novel functional organophosphorus compounds, transition-metal-catalyzed methods have been developed, which were previously considered difficult because of the strong bonding that occurs between transition metals and phosphorus. Addition reactions of triphenylphosphine and sulfonic acids to unsaturated compounds in the presence of a rhodium or palladium catalyst lead to phosphonium salts, in direct contrast to the conventional synthesis involving substitution reactions of organohalogen compounds. Rhodium and palladium complexes catalyze the cleavage of P–P bonds in diphosphines and polyphosphines and can transfer organophosphorus groups to various organic compounds. Subsequent substitution and addition reactions proceed effectively, without using a base, to provide various novel organophosphorus compounds.1 Introduction2 Transition-Metal-Catalyzed Synthesis of Phosphonium Salts by Addition Reactions of Triphenylphosphine and Sulfonic Acids3 Rhodium-Catalyzed P–P Bond Cleavage and Exchange Reactions4 Transition-Metal-Catalyzed Substitution Reactions Using Diphosphines4.1 Reactions Involving Substitution of a Phosphorus Group by P–P Bond Cleavage4.2 Related Substitution Reactions of Organophosphorus Compounds4.3 Substitution Reactions of Acid Fluorides Involving P–P Bond Cleavage of Diphosphines5 Rhodium-Catalyzed P–P Bond Cleavage and Addition Reactions6 Rhodium-Catalyzed P–P Bond Cleavage and Insertion Reactions Using Polyphosphines7 Conclusions

Transition metal-catalyzed reactions in heterocyclic chemistry

2002 ◽  
Vol 74 (8) ◽  
pp. 1327-1337 ◽  
Author(s):  
Irina P. Beletskaya
Keyword(s):  
Transition Metal ◽  
Heterocyclic Compounds ◽  
Heterocyclic Chemistry ◽  
Substitution Reactions ◽  
Multiple Bonds ◽  
Palladium Catalyzed ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

The palladium-catalyzed substitution reactions forming carbon­carbon and carbon­element bonds, as well as nickel-catalyzed addition of E­H and E­E' bonds across multiple bonds, are considered in their application to the chemistry of heterocyclic compounds.

Transition metal-catalyzed allylic substitution reactions with unactivated allylic substrates

2015 ◽  
Vol 44 (22) ◽  
pp. 7929-7967 ◽  
Author(s):  
Nicholas A. Butt ◽  
Wanbin Zhang
Keyword(s):  
Transition Metal ◽  
Allylic Substitution ◽  
Substitution Reactions ◽  
Recent Developments ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

This review highlights recent developments in the area of transition metal-catalyzed allylic substitution reactions with unactivated allylic substrates.

Iridium-catalyzed Z-retentive asymmetric allylic substitution reactions

Science ◽  
2021 ◽  
Vol 371 (6527) ◽  
pp. 380-386 ◽  
Author(s):  
Ru Jiang ◽  
Lu Ding ◽  
Chao Zheng ◽  
Shu-Li You
Keyword(s):  
Transition Metal ◽  
Optically Active ◽  
Promising Method ◽  
Allylic Substitution ◽  
Substitution Reactions ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed ◽  
Quaternary Stereocenter ◽  
Thermodynamic Instability

Z-Olefins are challenging synthetic targets owing to their relative thermodynamic instability. Transition metal–catalyzed asymmetric allylic substitution reactions are well known for installing stereocenters adjacent to branched or E-linear olefins. However, analogous reactions for the synthesis of optically active Z-olefin products are rare. Here we report iridium-catalyzed asymmetric allylic substitution reactions that retain Z-olefin geometries while establishing an adjacent quaternary stereocenter. The formation of transient anti-π-allyl-iridium intermediates and their capture by external nucleophiles before isomerization to the thermodynamically more stable syn-π-allyl-iridium counterparts have been observed. These results provide a promising method for preparing chiral Z-olefinic compounds.

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