Prodigiosin synthesis

Santer, U. V., and H. J. Vogel Prodigiosin synthesis in Serratia marcescens isolation of a pyrrole-containing precursor. Biochim. et Biophys. Acta. 19, 578 (1956). 

SiDDiQUi, M. A. Q., and G. E. Peterson Streptomycin and syntrophic prodigiosin synthesis in Serratia marcescens. Antonie van Leeuwenhoek. J. Microbiol. Serol. 31, 193 (1965). 

Morrison, D. A. Prodigiosin synthesis in mutants of Serratia marcescens. J. Bacteriol. 91, 1599 (1966). 

A key step in Boger s synthesis of prodigiosine and related compounds is the oxidative cyclization of dipyrrolyl ketones such as 35 to give 36 in excellent yield [35, 36]. Noteworthy is the use of polymer-supported Pd(OAc)2 in this chemistry. 

The first efficient application of a well-defined ruthenium indenylidene complex in metathesis was described in 1999 by Frirstner for the total synthesis of a cyclic prodigiosin derivative, a potential lead compound for the development of immunosuppressive agents. The RCM using the ruthenium indenylidene complex DC (10 mol%) as precatalyst leads to the transformation of the N-protonated diene into the desired macrocycle in 65% yield (Equation 8.8) [43]. 

Full details of the synthesis of metacycloprodigiosin (described in our original article have now appeared." Some 5-aryl-2,2 -pyrromethene analogs of prodigiosin" and a phenyl analog of metacycloprodigiosin have also been prepared. 0-alkylation of 3-hydroxypyrroles and 3-hydroxy pyrromethenones... 

Fiirstner, A. Grabowski, J. Lehmann. C.W. Kataoka. T. Nagai, K. Synthesis and biological evaluation of non-ylprodigiosin and macrocyclic prodigiosin analogues. Chembiochem 2001. 2 (1), 60-68. 

Here, these alkaloids will be described in this chapter as alkaloids based on a porphine skeleton. Their biosynthesis is completely different from that of prodigiosin described in the chapter on alkaloids derived from proline (Chapter 5). Total synthesis of chlorophyll a was achieved [2,3], and the assignment of all resonances in the nuclear magnetic resonance (NMR) spectrum of chlorophyll b has been accomplished [4]. Also the biosynthesis and chemistry of the chlorophylls have been reviewed [5—8]. 

Therefore, much effort has been directed toward the synthesis of compounds capable of the cotransport of HCl across lipid bilayer membranes. For example, Sessler and coworkers have studied the anion-binding and transport properties of prodigiosin model compounds 16-20 (Figure 8). " Binding studies conducted in acetonitrile solution by using ITC showed that the monoprotonated iodide salts of compounds 16-20 bound chloride with stability constants between 1.1 x 10 and 8.8 x 10 M at 30 °C. The crystal structure of the HCl complex of compound 20 was elucidated, showing chloride bound to the protonated receptor by three hydrogen bonds in... 

Boger, D.L. and M. Patel. 1987. Total synthesis of prodigiosin. Tetrahedron Lett... 

Boger, D.L. and M. Patel. 1988. Total synthesis of prodigiosin, prodigiosene, and des-methoxyprodigiosin Diels-Alder reactions of heterocyclic azadienes and development of an effective paUadium(ii)-promoted 2,2 -bipyrroUe coupling procedure. J Org Chem 53 1405-1415. 

Fig. 1. A, Pyrryldipyrrylmethene structure of prodigiosin confirmed by synthesis (Rapoport and Holden, i960, 1962) B, original tripyrrylmethene structure proposed by Wrede and Rothhaas (1934)...

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