Cyclopropanation Reactions Mediated by Group 9 Metal Porphyrin Complexes

Abstract

Keywords: Cyclopropanation / Diazo compounds / Porphyrins / Cobalt / Rhodium / IridiumThe one-pot reaction of diazo compounds with olefins represents a useful strategy to synthesise cyclopropanes, which are important both as starting materials for the synthesis of organic compounds and because of their intrinsic pharmaceutical properties. Herein we describe the catalytic activity of group 9 metal porphyrin complexes to cyclopropanate ole-

Thiosemicarbazone copper complexes as competent catalysts for olefin cyclopropanations

“…[CuHL 4 ] n (15) was collected as a light brown powder (90%). MS 6 ] n (17) was collected as a brown powder (51%).…”

“…As a result, great efforts have been made to develop efficient stereoselective methods for the synthesis of cyclopropanes [3]. A particularly versatile method is the metalcatalysed cyclopropanation of olefins with diazo compounds, for which several efficient homogeneous catalysts have been developed [4]. Nevertheless, the synthesis of these compounds remains a considerable challenge, especially due to their interesting biological properties as well as their use as starting materials and intermediates in organic synthesis.…”

The ligand influence in stereoselective carbene transfer reactions promoted by chiral metal porphyrin catalysts

“…Amongst metal complexes which are effective in activating diazo derivatives in the alkene cyclopropanation and functionalization of X-H bonds, metal porphyrins are very efficient because they couple a high catalytic activity with an excellent chemical stability. [15][16][17][18][19][20][21][22] Porphyrin ligands can be used to synthesise metal catalysts with very different electronic and steric characteristics thanks to the plethora of structural modifications which can be carried out on a porphyrin skeleton. In addition the presence of different axial ligand(s) onto the active transition metal can further expand the chemical versatility of this class of catalysts ( Figure 1).…”

Quantum-Сhemical Insight into the Reactivity of 5-Bromo-10,20-diaryl-porphyrins towards Nucleophiles

“…[1][2][3][4] Various approaches are developed for the preparation of functionalized porphyrins by introduction of the desired substituents in the precursors or modification of the porphyrin core. [3][4][5][6] Transition metalassisted cross-coupling reactions are widely used for porphyrin functionalization.…”

“…[1][2][3][4] Various approaches are developed for the preparation of functionalized porphyrins by introduction of the desired substituents in the precursors or modification of the porphyrin core. [3][4][5][6] Transition metalassisted cross-coupling reactions are widely used for porphyrin functionalization. [5,[7][8][9][10][11][12][13][14][15][16] Notwithstanding their versatility, the palladium-mediated cross-coupling reactions require expensive catalysts and ligands that is a limiting factor for their industrial use, in particular in the medical pharmacology.…”