Ruthenium-porphyrin-catalyzed carbenoid transfer reactions

Abstract

Ruthenium-porphyrins are effective catalysts for a wide variety of 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 azomethine ylide formation/1,3-dipolar cycloaddition, and halonium, sulfonium, or ammonium ylide formation/[2,3]-sigmatropic rearrangement reactions. Extensive studies have demonstrated that ruthenium-porphyrins exhibit high stability, high product turnover numbers, and remarkable selectivity in catalytic carbenoid transfer reactions. The catalysis has been successfully applied to the synthesis of organic building blocks and natural products, and to the modification of peptides and proteins. 1 Introduction 2 Catalyst Types 3 Cyclopropanation Reactions 4 Carbon-Hydrogen, Nitrogen-Hydrogen, and Sulfur-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]-Sigmatropic Rearrangement 6.4 Sulfonium or Ammonium Ylide Formation/[2,3]-Sigmatropic Rearrangement 7 Comparison of (Carbene)ruthenium-Porphyrin Complexes with Iron and Osmium Analogues 8 Conclusion. © 2010 Georg Thieme Verlag Stuttgart · New York.