Ruthenium-Porphyrin-Catalyzed Carbenoid Transfer Reactions

Abstract

R u t h e n i u m -P o r p h y r i n -C a t a l y z e d C a r b e n o i d T r a n s f e r R e a c t i o n s CongAbstract: 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.

Communication—Semi-Rigid Ru(II)Porphyrinate-Based Macrocyclic Receptor as Endotopic Catalyst for Carbene Transfer Reactions

“…4). In this reaction, EDA reacts with the Ru(II) ion to extrude an N 2 molecule to yield an electrophile αestercarbenoid intermediate, [41][42][43][44][45][46][47] which undergoes a nucleophile attack 54,55 by another EDA molecule to afford a double-bond after a second extrusion of an N 2 molecule. As already discussed above, carbene axial ligands can exercise strong kinetic trans-effects in Ru (II)porphyrinates.…”

“…In the present communication, we use macrocycle 1 as ligand for Ru(II) ions to prepare macrocyclic endotopic complexes with a more extensive catalytic scope as acyclic Ru(II)porphyrinates are known [41][42][43][44][45][46][47] to promote a wide variety of carbene transfer/insertion reactions such as cyclopropanation, 1,3-dipolar cycloadditions, X-H (X = C, N, O, and S) insertions, olefination of aldehydes in the presence of phosphines and dimerization of diazo synthons.…”

Intramolecular carbenoid ylide forming reactions of 2-diazo-3-keto-4-phthalimidocarboxylic esters derived from methionine and cysteine

“…Thus, rhodium(II)-catalysed decomposition of 2-diazo-6-methylthio-3-oxohexanoate 11a gave the stable six-ring sulfonium ylide 20 in practically quantitative yield. It has recently been reported that ruthenium(II) porphyrins are suitable catalysts for carbenoid sulfonium ylide formation as well [43]. In continuation of our comparative studies of dirhodium(II,II) tetracarboxylate and tetracarbonyldiruthenium(I,I) complexes [44], we found that the saccharinato complex [Ru 2 (CO) 5 [μ-sac) 2 ] 2 [45], the acetato complex [Ru 2 (CO) 4 (μ-OAc) 2 ] n and the trinuclear ruthenium(0) complex Ru 3 (CO) 12 (3 mol % of catalyst in each case) gave yields of 74, 69, and 49% for the conversion of 11a to 20 .…”