TY - JOUR
T1 - Reactions of Co(III)-coordinated ornithine
T2 - Towards inhibitors of the polyamine biosynthetic pathway
AU - Clarkson, Andrea J.
AU - Blackman, Allan G.
AU - Clark, Charles R.
AU - Sargeson, Alan M.
PY - 2009
Y1 - 2009
N2 - Treatment of the complex ,Δ-Λ[Co(en)2(S-ornithineH- κ2N,O)](CF3SO3)3 with SOCl2 in DMF gives a mixture of the expected imino complex [Co(en)2(2-iminoornithineH-2N,O)]3+ and the amidine complex [Co(en)2(5-{[(1E)-(dimethylamino)methylene]amino}-2- iminopentanoate-2N,O)]3+, which is proposed to result from the reaction of the Vilsmeier reagent [ClCH=N(CH3)2] + with the terminal amine of coordinated ornithine. Treatment of the imino complex with nitromethane in alkaline solution gives the complex [Co(en)2(2-nitromethylornithineH-κ2N,O)] 3+, which contains the potential suicide inhibitor 2-nitromethylornithine. X-ray crystal structures of Δ-[Co(en) 2(S-ornithineH-κ2N,O)]Br3 and Δ,Λ-[Co(en)2(5-{[(1E)-(dimethylamino)methylene]amino}-2- iminopentanoate-κ2N,O)](ClO4)3 are reported.
AB - Treatment of the complex ,Δ-Λ[Co(en)2(S-ornithineH- κ2N,O)](CF3SO3)3 with SOCl2 in DMF gives a mixture of the expected imino complex [Co(en)2(2-iminoornithineH-2N,O)]3+ and the amidine complex [Co(en)2(5-{[(1E)-(dimethylamino)methylene]amino}-2- iminopentanoate-2N,O)]3+, which is proposed to result from the reaction of the Vilsmeier reagent [ClCH=N(CH3)2] + with the terminal amine of coordinated ornithine. Treatment of the imino complex with nitromethane in alkaline solution gives the complex [Co(en)2(2-nitromethylornithineH-κ2N,O)] 3+, which contains the potential suicide inhibitor 2-nitromethylornithine. X-ray crystal structures of Δ-[Co(en) 2(S-ornithineH-κ2N,O)]Br3 and Δ,Λ-[Co(en)2(5-{[(1E)-(dimethylamino)methylene]amino}-2- iminopentanoate-κ2N,O)](ClO4)3 are reported.
UR - http://www.scopus.com/inward/record.url?scp=70350102809&partnerID=8YFLogxK
U2 - 10.1071/CH09315
DO - 10.1071/CH09315
M3 - Article
SN - 0004-9425
VL - 62
SP - 1221
EP - 1225
JO - Australian Journal of Chemistry
JF - Australian Journal of Chemistry
IS - 10
ER -