Synthesis and chemical reactivity of new zinc porphyrin diazoacetates catalyzed by ruthenium and iron porphyrins

Iron: A Worthy Contender in Metal Carbene Chemistry

“…The latter revealed a vast scope of compatible alkenes, including vinyl ferrocene and a steroid derivative (33) , with great yields and selectivity (over 20:1 for all substrates). , Finally, iron porphyrins were used for the functionalization of porphyrin ligands themselves. The reaction of ZnTPP with EDA formed a mixture of cyclopropanation and the Buchner reaction products in poor yields, and the transesterification of EDA with a hydroxylated ZnTPP derivative formed a unique diazo reagent for coupling with styrene, thiols, or amines in good yields …”

“…The reaction of ZnTPP with EDA formed a mixture of cyclopropanation and the Buchner reaction products in poor yields, 54 and the transesterification of EDA with a hydroxylated ZnTPP derivative formed a unique diazo reagent for coupling with styrene, thiols, or amines in good yields. 55 Other iron tetrapyrrolic macrocycles were tested in carbene transfer. The Gross group performed extensive work on Fe III and Fe IV corroles bearing several axial ligands (Cl, OEt, Pyridine, NO) for styrene and EDA cyclopropanation with good yields but poor stereocontrol.…”

Carbene-Type Species in the Functionalization of Porphyrin Derivatives

“…14 In 2016, Simonneaux reported on the functionalization of porphyrins through carbene insertion via decomposition of diazo compounds. 15 Zinc porphyrin diazoacetates 9 and 10 ( Figure 4) were efficiently synthesized by reaction of the corresponding bromoacetates with N,N′-ditosylhydrazine.…”

Synthesis, crystal structure, catalytic dimerization and S H insertion of new porphyrin diazoketones

“…Surprisingly, simple diazoketone substituted meso-tetraphenyl-porphyrin have not been yet prepared. As part of a program investigating porphyrin diazocarbonyl methodologies [4][5][6][7][8], we have studied the functionalization of tetraarylporphyrin using trimethylsilyldiazomethane as reactive intermediates. Herein we report the synthesis of several diazoketone functionalized porphyrins and their chemical reactivity.…”