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DOI: 10.1039/A809858A (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 1, 1999, 879-888

Biosynthesis of porphyrins and related macrocycles. Part 51.1,2 Proof that a reductive step occurs during the biosynthesis of vitamin B12 by the microaerophilic organism, Propionibacterium shermanii

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Koji Ichinose, Masahito Kodera, Finian J. Leeper and Alan R. Battersby

Abstract

5-Amino[4-13C]laevulinic acid has been synthesised for enzymic conversion into 13C-labelled precorrin-2 12a. This was incubated with an enzyme system from Propionibacterium shermanii in the presence of [4-2H2]NADH 5a and [4-2H2]NADPH 6a to yield cobyrinic acid 15a, shown to carry 2H at C-19 by appropriate 13C-NMR studies. The same reducing cofactors but now stereospecifically labelled at C-4 with tritium were similarly used to biosynthesise cobyrinic acid which was 3H-labelled (15b) from the 4(R)-cofactors but carried no 3H (15c) when the 4(S[hair space])-cofactors were used. Suitable degradation of the cobyrinic acid 15b after conversion into its ester 16b proved 3H-labelling at C-19. These results establish that the biosynthesis of vitamin B12 in the microaerophilic organism Pr. shermanii involves a reductive step in which a reductase enzyme transfers 4-HR of the cofactor to C-19 of the macrocycle.

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