Diazo ester insertion in NH bonds of amino acid derivatives and insulin catalyzed by water-soluble iron and ruthenium porphyrin complexes (FeTSPPCl) as application of carbenoid transfer in aqueous media

Abstract

a b s t r a c tThe metal complex FeTSPPCl (5,10,15,20-tetrakis)-(4-sulfonato-phenyl)-porphyrin-iron(III) chloride is an active catalyst for carbenoid insertion in N H bonds of aminoacid derivatives in aqueous media. A variety of diazoacetates and methyl diazophosphonate were used as carbenoid precursors. The commercially available iron porphyrin complex can also selectively catalyze alkylation of the N-terminus of insulin (chain B).

Carbene Transfer Reactions Catalysed by Dyes of the Metalloporphyrin Group

“…Most recently, Simonneaux and co-workers described the intermolecular N-H insertion of different aminoacid esters (tryptophan, phenylalanine, tyrosine) using various diazo esters (ethyl diazoacetate, diisopropyl diazomethylphosphonate, 4-(trifluoromethyl)benzyl diazoacetate and 4-(thiomethyl)benzyl diazoacetate) catalysed by Fe(TPP)Cl and by the water-soluble Ru(TPPS)(CO) and Fe(TPPS)Cl ( Figure 2 ). Moreover, the site selective modification of terminal NH 2 group of insulin was also accomplished by using the water-soluble Fe(TPPS)Cl as catalyst, the insertion being regioselective onto the NH 2 termini of insulin [ 91 ].…”

Carbene Transfer and Carbene Insertion Reactions Catalyzed by a Mixed‐Ligand Copper(I) Complex

“…For instance, cyclopropanes, obtained from the carbene transfer to differently substituted olefin double bonds, are versatile intermediates that can be converted into a variety of useful products by cleavage of the strained three‐membered ring . Similarly, transition‐metal‐catalyzed insertion of carbenes into heteroatom–hydrogen bonds (X–H) leads to α‐amino esters, α‐amino ketones, and nitrogen‐containing heterocycles (X = N), or α‐alkoxy, α‐aryloxy, and α‐hydroxy esters, together with a variety of oxygen‐containing heterocyclic compounds (X = O) . These carbene transfer reactions are promoted by several metals, for instance rhodium, iron, ruthenium, gold, or copper …”

Organometallic catalysis in aqueous and biological environments: harnessing the power of metal carbenes

“…FeTSPPCl also proved to be an effective catalyst for site-selective modification of the terminal NH 2 group of insulin using EDA, and a PBS/acetonitrile (7 : 4) mixture as reaction media, with 90% conversion after 1 h. In this case, 10% of the double insertion product was detected. 72 …”