Open AccessRing contraction of hydroporphinoid to corrinoid complexes
Author(s) -
Vittorio Rasetti,
Andreas Pfaltz,
Christoph Kratky,
Albert Eschenmoser
Publication year - 1981
Publication title -
proceedings of the national academy of sciences of the united states of america
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.011
H-Index - 771
eISSN - 1091-6490
pISSN - 0027-8424
DOI - 10.1073/pnas.78.1.16
Subject(s) - corrinoid , corrin , chemistry , nickel , porphyrin , stereochemistry , ring (chemistry) , contraction (grammar) , medicinal chemistry , organic chemistry , biochemistry , methylation , methyltransferase , gene , medicine
Crystalline nickel(II) and dicyanocobalt(III) complexes of a racemic 1,2,2,7,7,12,12,17,17,20-decamethyl-20-hydroxy-1,2,3,7,8,12,13,20-octahydro- 17H -porphyrin rearrange to the corresponding complexes of racemic 19-acetyl-1,2,2,7,7,12,12,17,17-nonamethyl-trans -corrin on melting (approximately 290°C and 260°C, respectively). The nickel(II) 19-acetylcorrinate formed in this way is shown to deacetylate to racemic nickel(II) 1,2,2,7,7,12,12,17,17-nonamethyl-trans -corrinate on treatment with 2 M KOH. These reactions are being studied as potentially biomimetic chemical models for the elusive ring contraction step in vitamin B12 biosynthesis.