Model studies for the thiol-mediated methyl transfer to corrinoids.
The thiol-dependent methylation of heptamethyl cob(II)yrinate 8r with methyl iodide and methyl tosylate was explored under a variety of conditions. The interaction of the heptamethyl cob(II)yrinate with a variety of thiols was monitored prior to the addition of the methylating agent, and the formation of the Co(I) complex was only apparent in the reaction with hexane thiol. Nevertheless, thiol-mediated methylation of the Co(II) complex 8r takes place with methyl iodide under most conditions. The Co-methylation with methyl tosylate showed a different reactivity, was inhibited by pyridine or N-methylimidazole, and was strongly dependent on the the acidity of the thiol used. Mechanistic aspects are discussed.
Wedemeyer-Exl
Christina
C
Department of Chemistry and Biochemistry, University of Bern, Freiestr. 3, 3012, Bern, Switzerland.
Darbre
Tamis
T
Keese
Reinhart
R
D000478:Alkylation; D002021:Buffers; D045728:Corrinoids / Q000737:chemistry*; D005978:Glutathione / Q000737:chemistry; D008745:Methylation; D008956:Models, Chemical; D015394:Molecular Structure; D010091:Oximes / Q000737:chemistry; D010636:Phenols / Q000737:chemistry; D012996:Solutions; D013057:Spectrum Analysis; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D002021:Buffers; D045728:Corrinoids; D010091:Oximes; D010636:Phenols; D012996:Solutions; D013438:Sulfhydryl Compounds; C042983:thiophenol; D005978:Glutathione; C005732:thioacetic acid