Nucleophilic Cyclopropane Ring Opening in Duocarmycin SA Derivatives by Methanol under Acid Conditions: A Quantum Mechanical Study in the Gas-Phase and in Solution
Nucleophilic Cyclopropane Ring Opening in Duocarmycin SA Derivatives by Methanol under Acid Conditions: A Quantum Mechanical Study in the Gas-Phase and in Solution(369 views visite) Cimino P, Improta R, Bifulco G, Riccio R, Gomez-paloma L, Barone V
Dipartimento di Chimica, Università Federico II, Complesso Univ. Monte S.Angelo, via Cintia, I-80126 Napoli, Italy Dipto. di Scienze Farmaceutiche, Università di Salerno, via Ponte don Melillo, 84084, Fisciano (SA), Italy Ist. di Biostrutture e Bioimmagini, CNR,M, via Mezzocannone 6, I-80134 Napoli, Italy
Baraldi, P.G., Balboni, G., Pavani, M.G., Spalluto, G., Tabrizi, M.A., De Clercq, E., Balzarini, J., Romagnoli, R., (2001) J. Med. Chem., 44, pp. 2536-2543
Nagamura, S., Asai, A., Kobayashi, E., Gomi, K., Saito, H., (1997) Bioorg. Med. Chem., 5, pp. 623-630
Amishiro, N., Nagamura, S., Kobayashi, E., Okamoto, A., Gomi, K., Okabe, M., Saito, H., (2000) Bioorg. Med. Chem., 8, pp. 1637-1643
Boger, D.L., Goldberg, J.A., McKie, A., (1996) Bioorg. Med. Chem. Lett., 6, pp. 1955-1960
Boger, D.L., Santillan Jr., A., Searcey, M., Jin, Q., (1999) J. Org. Chem., 64, pp. 5241-5244
Boger, D.L., Wysocki Jr., R.J., Ishizaki, T., (1990) J. Am. Chem. Soc., 112, pp. 5230-5240
Boger, D.L., Mesini, P., (1994) J. Am. Chem. Soc., 116, pp. 11335-11348
Boger, D.L., Garbaccio, R.M., (1999) J. Org. Chem., 64, pp. 5666-5669
Kock, W., Holthousen, W.C., (2000) A Chemist's Guide to Density Functional Theory, , Wiley-VCH: Weinheim
Adamo, C., Cossi, M., Rega, N., Barone, V., (2001) Theoretical Biochemistry: Processes and Properties of Biological Systems. Theoretical and Computational Chemistry, 9. , Elsevier: New York
Parr, R.G., Szentpaly, L., Liu, S., (1999) J. Am. Chem. Soc., 121, pp. 1922-1924
Chermette, H., (1999) J. Comput. Chem., 20, pp. 129-154
Parr, R., Pearson, R.G., (1983) J. Am. Chem. Soc., 105, pp. 7512-7516
Pearson, R.G., (1997) Chemical Hardness, , VCH: Weinheim
Ciofini, I., Hazebroucq, S., Joubert, L., Adamo, C., (2004) Theor. Chem. Acc., , in press
Warpehoski, M.A., Harper, D.E., (1994) J. Am. Chem. Soc., 116, pp. 7573-7580
Boger, D.L., Machiba, K., Hertzog, D.L., Kitos, P.A., Holmes, D., (1993) J. Am. Chem. Soc., 115, pp. 9025-9036
Boger, D.L., Turnbull, P., (1998) J. Org. Chem., 63, pp. 8004-8011
Baird, R., Winstin, S., (1962) J. Am. Chem. Soc., 85, pp. 567-578
Del Rio, E., Menendez, M.I., Lopez, R., Sordo, T.L., (2000) J. Phys. Chem. A, 104, pp. 5568-5571
Boger, D. L., Johnson, D. L., (1996) Angew. Chem., Int. Ed. Engl., 35, pp. 1438-147
Boger, D. L., Hertzog, D. L., Bollinger, B., Johnson, D. L., Cai, H., Goldberg, J., Turnbull, P., (1997) J. Am. Chem. Soc., 119, pp. 4977-4986
Boger, D. L., Bollinger, B., Hertzog, D. L., Johnson, D. L., Cai, H., Mesini, P., Garbaccio, R. M., Kitos, P. A., (1997) J. Am. Chem. Soc., 119, pp. 4987-4998
Baraldi, P. G., Balboni, G., Pavani, M. G., Spalluto, G., Tabrizi, M. A., De Clercq, E., Balzarini, J., Romagnoli, R., (2001) J. Med. Chem., 44, pp. 2536-2543
Boger, D. L., Goldberg, J. A., McKie, A., (1996) Bioorg. Med. Chem. Lett., 6, pp. 1955-1960
Boger, D. L., Santillan Jr., A., Searcey, M., Jin, Q., (1999) J. Org. Chem., 64, pp. 5241-5244
Boger, D. L., Wysocki Jr., R. J., Ishizaki, T., (1990) J. Am. Chem. Soc., 112, pp. 5230-5240
Boger, D. L., Mesini, P., (1994) J. Am. Chem. Soc., 116, pp. 11335-11348
Boger, D. L., Garbaccio, R. M., (1999) J. Org. Chem., 64, pp. 5666-5669
Boger, D. L., Boyce, C. W., Johnson, D. L., (1997) Bioorg. Med. Chem. Lett., 7, pp. 233-238
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Montgomery Jr., J. A., Pople, J. A., (2003) Gaussian 03, Revision B. 4, , Gaussian, Inc., Pittsburgh, PA
Foresman, J. B., Frisch, A. E., (1996) Exploring Chemistry with Electronic Structure Methods, 2nd Ed., , Gaussian Inc.: Pittsburgh, PA
Reed, A. E., Curtiss, L. A., Weinhold, F., (1988) Chem. Rev., 88, pp. 899-926
Parr, R. G., Szentpaly, L., Liu, S., (1999) J. Am. Chem. Soc., 121, pp. 1922-1924
Pearson, R. G., (1997) Chemical Hardness, , VCH: Weinheim
Warpehoski, M. A., Harper, D. E., (1994) J. Am. Chem. Soc., 116, pp. 7573-7580
Boger, D. L., Machiba, K., Hertzog, D. L., Kitos, P. A., Holmes, D., (1993) J. Am. Chem. Soc., 115, pp. 9025-9036
Boger, D. L., Turnbull, P., (1998) J. Org. Chem., 63, pp. 8004-8011
Nucleophilic Cyclopropane Ring Opening in Duocarmycin SA Derivatives by Methanol under Acid Conditions: A Quantum Mechanical Study in the Gas-Phase and in Solution
We present a quantum-mechanical study of the SN2 acid-catalyzed solvolysis with methanol of seven simplified duocarmycin SA (DNA alkylating agent) derivatives characterized by spirocyclic systems of increasing complexity, all containing the cyclopropyl/cyclohexadienone substrate. The reaction has been studied at the DFT-PBE0/6-31G(d) level in the gas phase and in methanol solution, using in the latter case the polarizable continuum model (PCM) to describe solvent effects. The results delivered by this computational protocol are in full agreement with the available experimental evidences and are not modified by extension of the basis set or by using a second-order many-body treatment (MP2) in place of DFT. This allows investigation of substituent effects in terms of structure/reactivity relationships and evaluation of the role of stereoelectronic effects. Furthermore, reactivity indices (hardness, electrophilicity) have been computed and shown to correlate well with activation energies. Together with their intrinsic interest, the details of the mechanism of the acid-catalyzed nucleophilic addition to the activated cyclopropane issuing from the present study pave the route for a deeper understanding of the molecular basis for the remarkable profile of the DNA-alkylation by DSA derivatives.
Nucleophilic Cyclopropane Ring Opening in Duocarmycin SA Derivatives by Methanol under Acid Conditions: A Quantum Mechanical Study in the Gas-Phase and in Solution
Nucleophilic Cyclopropane Ring Opening in Duocarmycin SA Derivatives by Methanol under Acid Conditions: A Quantum Mechanical Study in the Gas-Phase and in Solution
Testino G, Leone S, Fagoonee S, Del Bas JM, Rodriguez B, Puiggros F, Marine S, Rodriguez MA, Morina D, Armengol L, Caimari A, Arola L, Cimini FA, Barchetta I, Carotti S, Bertoccini L, Baroni MG, Vespasiani-gentilucci U, Cavallo MG, Morini S, Nelson JE, Roth CL, Wilson LA, Yates KP, Aouizerat B, Morgan-stevenson V, Whalen E, Hoofnagle A, Mason M, Gersuk V, Yeh MM, Kowdley KV, Lee SM, Jun DW, Cho YK, Jang KS, Kucukazman M, Ata N, Dal K, Yeniova AO, Kefeli A, Basyigit S, Aktas B, Akin KO, Agladioglu K, Ure OS, Topal F, Nazligul Y, Beyan E, Ertugrul DT, Catena C, Cosma C, Camozzi V, Plebani M, Ermani M, Sechi LA, Fallo F, Goto Y, Ray MB, Mendenhall CL, French SW, Gartside PS Serum vitamin A deficiency and increased intrahepatic expression of cytokeratin antigen in alcoholic liver disease(427 visite) Hepatology (ISSN: 1827-1669electronic, 0026-4806linking), 1988 Sep; 83120693611123109(5): 1019-1026. Impact Factor:0.913 DettagliEsporta in BibTeXEsporta in EndNote
281 Records (265 escludendo Abstract e Conferenze). Impact factor totale: 1161.591 (1106.117 escludendo Abstract e Conferenze). Impact factor a 5 anni totale: 1219.916 (1158.388 escludendo Abstract e Conferenze).
Last modified by Ultima modifica di Marco Comerci on in data Sunday 12 July 2020, 13:15:11 369 views visite. Last view on Ultima visita in data Friday 22 January 2021, 13:39:36