126581-06-4Relevant academic research and scientific papers
A new general method for selective β-polynitration of porphyrins; preparation and redox properties of Zn-porphyrins bearing one through to eight β-nitro substituents and X-ray structure of the first Zn β-pernitro porphyrin
Palacio,Mansuy-Mouries,Loire,Le Barch-Ozette,Leduc,Barkigia,Fajer,Battioni,Mansuy
, p. 1907 - 1908 (2007/10/03)
Selective β-polynitration of Zn-5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin, Zn(TDCPP), is achieved by controlled titration with the HNO3-CF3SO3H-(CF3SO2)2O system, and affords a full series of Zn porphyrins bearing one through to eight β-nitro groups in high yield and exhibiting a wide range of reduction potentials (from -920 to +155 mV vs. SCE); an X-ray structure of the first reported β-pernitrated Zn porphyrin Zn(TDCPN8P)(EtOH)2·2EtOH confirms the synthetic methodology.
Suicide inactivation of cytochrome P-450 model compounds by terminal olefins. 2. Steric and electronic effects in heme N-alkylation and epoxidation
Collman, James P.,Hampton, Philip D.,Brauman, John I.
, p. 2986 - 2998 (2007/10/02)
This paper reports a continuation of our study of synthetic hemins as models for the suicide inactivation of P-450 by 1-alkenes. The branching between epoxidation and heme N-alkylation, as measured by the partition number, has been studied as a function of the steric and electronic properties of substituted styrenes and of several chloro(tetraarylporphyrin)iron catalysts. Partition numbers exhibit only a modest sensitivity to steric properties of the catalyst and are relatively insensitive to the electronic properties of both the catalyst and the olefin. N-Alkylporphyrins isolated from the epoxidation of terminal alkenes by three of these hemins show the same regiochemistry as the N-alkylporphyrins reported for P-450. On the basis of the stereochemistry of epoxidation and N-alkylation, the insensitivity of the partition numbers to electronic effects, and the relative reactivities of terminal alkenes, we discuss various possibilities for the mechanism of epoxide and N-alkylhemin formation.
