Search results for "Iron catalyzed"
showing 8 items of 8 documents
Front Cover: Iron-Catalyzed C−O Bond Activation: Opportunity for Sustainable Catalysis (ChemSusChem 20/2017)
2017
Iron-Catalyzed C−O Bond Activation: Opportunity for Sustainable Catalysis
2017
Oxygen-based electrophiles have emerged as some of the most valuable cross-coupling partners in organic synthesis due to several major strategic and environmental benefits, such as abundance and potential to avoid toxic halide waste. In this context, iron-catalyzed C-O activation/cross-coupling holds particular promise to achieve sustainable catalytic protocols due to its natural abundance, inherent low toxicity, and excellent economic and ecological profile. Recently, tremendous progress has been achieved in the development of new methods for functional-group-tolerant iron-catalyzed cross-coupling reactions by selective C-O cleavage. These methods establish highly attractive alternatives t…
Ligand Effect on Iron-Catalyzed Cross-Coupling Reactions: Evaluation of Amides as O-Coordinating Ligands
2019
The development of new highly efficient O‐coordinating ligands for iron‐catalyzed C(sp2)−C(sp3) cross‐coupling reactions is reported. A structure‐reactivity study on the effect of amides as ligands in the industrially‐important iron‐catalyzed cross‐coupling of aryl chlorides with challenging organometallics possessing β‐hydrogens was performed. Investigation of a series of new 21 ligands that rationally vary in O‐coordination aptitude as well as sterics around the amide bond pinpointed the features that are important for catalysis. The study led to the discovery of several highly efficient ligands for cross‐coupling, including TMU (TMU=tetramethylurea), N‐cyclic and coordinating benzamides.…
Iron‐Catalyzed Cross‐Couplings in the Synthesis of Pharmaceuticals: In Pursuit of Sustainability
2018
The scarcity of precious metals has led to the development of sustainable strategies for metal-catalyzed cross-coupling reactions. The establishment of new catalytic methods using iron is attractive owing to the low cost, abundance, ready availability, and very low toxicity of iron. In the last few years, sustainable methods for iron-catalyzed cross-couplings have entered the critical area of pharmaceutical research. Most notably, iron is one of the very few metals that have been successfully field-tested as highly effective base-metal catalysts in practical, kilogram-scale industrial cross-couplings. In this Minireview, we critically discuss the strategic benefits of using iron catalysts a…
N-Methylcaprolactam as a Dipolar Aprotic Solvent for Iron-Catalyzed Cross-Coupling Reactions: Matching Efficiency with Safer Reaction Media
2019
Although iron‐catalysis provides a powerful alternative to the more conventional palladium and nickel in the cross‐coupling arena, the major limitation is the necessity for carcinogenic N‐methylpyrrolidone as a co‐solvent in the vast majority of catalytic reactions. Herein, we introduce N‐methylcaprolactam as an efficient, non‐toxic and practical dipolar aprotic solvent for iron‐catalyzed C(sp2)−C(sp3) alkylative cross‐coupling of aryl chlorides and tosylates. The utility of this method is reflected by its wide substrate scope, high yields and capacity to cross‐couple challenging alkyl organometallics prone to b‐hydride elimination and homocoupling. Considering the broad utility of iron‐cat…
Iron-Catalyzed C(sp2)–C(sp3) Cross-Coupling of Chlorobenzenesulfonamides with Alkyl Grignard Reagents: Entry to Alkylated Aromatics
2018
Alkylated benzosulfonamides are compounds of high importance in organic synthesis, including the production of pharmaceuticals, agrochemicals, and plasticizers. We report the iron-catalyzed C(sp2)–C(sp3) cross-coupling of chlorobenzosulfonamides with alkyl Grignard reagents under mild and sustainable conditions. Electronically and sterically varied benzosulfonamides as well as challenging alkyl organometallics containing β-hydrogen afford alkylated benzosulfonamides in high to excellent yields. Sulfonamide represents the most reactive activating group for iron-catalyzed cross-coupling. The process affords alkylated benzenesulfonamides poised for medicinal chemistry applications and traceles…