Ruthenium-Porphyrin-Catalyzed Carbenoid Transfer Reactions

Abstract

Ruthenium-porphyrins are effective catalysts for a wide varietyof carbenoid transfer reactions, such as alkene cyclopropanation,carbon-hydrogen, nitrogen-hydrogen, or sulfur-hydrogen (X-H,X = C, N, S) bond insertion, diazo coupling, carbonyl or azomethineylide formation/1,3-dipolar cycloaddition, and halonium,sulfonium, or ammonium ylide formation/[2,3]-sigmatropicrearrangement reactions. Extensive studies have demonstrated that ruthenium-porphyrinsexhibit high stability, high product turnover numbers, and remarkableselectivity in catalytic carbenoid transfer reactions. The catalysishas been successfully applied to the synthesis of organic buildingblocks and natural products, and to the modification of peptidesand proteins. 1 Introduction 2 Catalyst Types 3 Cyclopropanation Reactions 4 Carbon-Hydrogen, Nitrogen-Hydrogen, andSulfur--Hydrogen Bond Insertion Reactions 5 Alkene Formation Reactions 5.1 Coupling of Diazo Compounds 5.2 Olefination of Aldehydes 6 Ylide Formation and Subsequent Reactions 6.1 Carbonyl Ylide Formation/1,3-Dipolar Cycloaddition 6.2 Azomethine Ylide Formation/1,3-Dipolar Cycloaddition 6.3 Halonium Ylide Formation/[2,3]-SigmatropicRearrangement 6.4 Sulfonium or Ammonium Ylide Formation/[2,3]-SigmatropicRearrangement 7 Comparison of (Carbene)ruthenium-Porphyrin Complexes withIron and Osmium Analogues 8 Conclusion