TTQ-2004-Seminar.pptVIP

* * Regioselectivity for Condensation Reactions of Qunonoid Models of Tryptophan Tryptophylquinone (TTQ). A Density Functional Theory Study Jian-Wei Zou Key Lab for Molecular Design and Nutrition Engineering, Ningbo Institute of Technology, Ningbo, China Background: Oxidative deamination of amine “Corey’s reagent”, which is “Biomimetic”, appears to be the most effective synthetic reagent to date for the reaction JOC, 1988, 5994 A number of Enzymes e.g., methylamine dehydrogenase (MADH) and aromatic amine dehydrogenase (AADH) can implement the conversion readily Cofactor of the enzyme Aims of the present work: y Structure information one the TTQ cofactor and its model compounds y The regioselectivity of the condensation step and the structure-regioselectivity relationship y Preliminary study of the catalytic effect of PQQ superior to TTQ Amine Amine Amine Structure of 3-methyl-4-(3-methyl-1H-2-indolyl)-6,7-dihydro-1H-6,7-indoledione (IIQ) The differences in the part of geometries around the polar quinone group are slightly larger, which can be due to the occurrence of water near this area in the MADH crystal structure. (c) The potential energy surface of IIQ along the dihedral angle c 123.5° (0.74 kcal/mol) 49.6° (0.00 kcal/mol) 97.9° (1.71 kcal/mol) IIQ is flexible for the rotation of inter-indole ring as the difference of the total energy is within 1.0 kcal/mol at a range of the dihedral angle from 30 to 75°. The origin of regioselectivity 1. The space restriction at the enzyme active site Chen et al. FEBS Lett. 1991, 287, 163. 2. The difference of the thermodynamic stability of the carbinolamine intermediate (PM3 calculation) Itoh et al. JOC, 1996, 61, 8967. This argument was challenged by recent studies by Itoh et al. who found that the regioselectivity also existed in the model systems. 3. Possible factors (the present work) The difference in electronic structures of the two carbonyl groups The difference in thermodyna