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(497 views) 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
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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
Kállay C, Dávid A, Timári S, Nagy EM, Sanna D, Garribba E, Micera G, De Bona P, Pappalardo G, Rizzarelli E, Sóvágó I * Copper(II) complexes of rat amylin fragments(360 views) Dalton T (ISSN: 1477-9234, 1477-9226, 1477-9234electronic), 2011 Oct 14; 40(38): 9711-9721. Impact Factor:3.838 ViewExport to BibTeXExport to EndNote
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(616 views) Hepatology (ISSN: 1827-1669electronic, 0026-4806linking), 1988 Sep; 83120693611123109(5): 1019-1026. Impact Factor:0.913 ViewExport to BibTeXExport to EndNote
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