Application of Metal Phthalocyanine complexes to Carbene Transfer to N-H Bonds and Olefins

Carbene transfer to olefins and X-H bonds via α-diazocarbonyl precursor decomposition is a useful tool to build potentially biologically relevant elaborated molecules. Among metal complexes, metalloporphyrins have been extensively studied as catalysts for carbene transfer reactions. In contrast, their phthalocyanine counterparts have been used rarely but their utilization as catalyst for the elaboration of complex molecules is a growing area of interest. Here we present the novel use of binuclear Ruthenium(IV) phthalocyanine and Iron(III) phthalocyaninate bearing crown ether substituents as catalysts for the insertion of carbene formed from ethyl diazoacetate precursor into N-H bonds. Ruthenium(IV) phthalocyanine was also studied for the first time for intermolecular cyclopropanation of various olefins. With [(15C5)4PcFe]Cl as a catalyst for the synthesis of new class of ethyl glycinate amino acid derivatives, turnover numbers up to 3360 have been achieved. 36 – 69 % yields were obtained in the case of single N-H insertion products and up to 77 % in the case of double N-H insertion products.