38559-35-2Relevant academic research and scientific papers
Marcus Theory of Hydride Transfer from an Anionic reduced Deazaflavin to NAD+ Analogues
Lee, In-Sook Han,Ostovic, Drazen,Kreevoy, Maurice
, p. 3989 - 3993 (2007/10/02)
Eighteen rate constants, kij for hydride transfer from the conjugate base of 1,5-dihydro-3,10-dimethyl-5-diazaisoalloxazine to a variety of pyridinium, quinolinium, phenanthridinium, and acridinium ions have been determined. (All the oxidizing agents can be regarded as analogues of NAD+.) The kij values span 7 powers of 10 and the corresponding equilibrium constants, Kij, span more than 13 powers of 10.For reactions with ΔG0 near zero, the kij values are close to those given by modified Marcus theory (ref 10).However, with more negative ΔG0 values, the observed kij increase more strogly than the calculated values.Agreement can be produced by making the standard free energy of precursor complex formation, symbolized WT +- here, to indicate that it applies to reactants of opposite charge, a linear function of ΔG0, and treating the slope and interrcept of the linear relation as adjustable parameters.The best fit is obtained with WT+-(in kJ*mol-1)=-9.4+0.11ΔG0.An avarage discrepancy between calculated and observed ln kij values of 0.5 is achieved, which is a good as the overall fit achieved for hydride transfer from neutral NADH analogues to NAD+ analogues (ref 10).The form and the parameterization of Wf are shown to be a physically reasonable approximation for reactions with ΔG00.These results strengthen the conclusion (ref 10) that a wide range of hydride transfer rates can be quantitavely understood without introducing high-energy metastable intermediates (radicals and radical ions).
Hydride Transfer and Oxyanion Addition Equilibria of NAD+ Analogues
Ostovic, Drazen,Lee, In-Sook Han,Roberts, Roger M. G.,Kreevoy, Maurice M.
, p. 4206 - 4211 (2007/10/02)
Equilibrium constants, K, have been determined for the reduction of 10-methylacridinium ion by 15 N-heterocyclic hydride donors: acridine, quinoline, pyridine, and phenanthridine derivatives.The solvent was a mixture of 2-propanol and water in the ratio 4 : 1 by volume.Reduction potentials have been estimated for the corresponding cations in aqueous solution by assuming that the K's would be the same and accepting -361 mV as the reduction potential of the 3-(aminocarbonyl)-1-benzylpyridinium ion.These reduction potentials span 430 mV.Values of pKR have also been determined for six of the cations in the same solvent.For derivatives of the same ring system, -ΔlogK is approximately equal to ΔpKR, but a 4 log unit discrepancy appears when phenanthridine derivatives are compared with the 9-methylacridinium ion.
A Novel Synthesis of Pyrimidoquinoline-2(3H),4(10H)-diones (5-Deazaflavins) and Analogues by the Oxidative Cyclization of 5,5'-Arylmethylenebis-(6-alkylamino-3-methyluracils)
Yoneda, Fumio,Mori, Kenya,Sakuma, Yoshiharu,Yamaguchi, Hiroyuki
, p. 978 - 981 (2007/10/02)
The oxidative coupling of 5,5'-arylmethylenebis-(6-alkylamino-3-methyluracils), prepared by the condensation of 6-alkylamino-3-methyluracils and arenecarbaldehydes, with diethyl azodiformate afforded the corresponding pyrimidoquinoline-2(3H),4(10H)
