Mechanism, kinetics and selectivity of selenocyclization of 5-alkenylhydantoins: an experimental and computational study
作者： Biljana M Šmit , Radoslav Z Pavlović , Dejan A Milenković , Zoran S Marković
DOI: 10.3762/BJOC.11.200
关键词: Computational chemistry 、 Bicyclic molecule 、 Electrophilic addition 、 Chemistry 、 Regioselectivity 、 Organic chemistry 、 Double bond 、 Transition state 、 Deprotonation 、 Reaction mechanism 、 Nucleophile
摘要: The mechanism and selectivity of a bicyclic hydantoin formation by selenium-induced cyclization are investigated. proposed involves the intermediates formed an electrophilic addition selenium reagent on double bond starting 5-alkenylhydantoin prior cyclization. These readily converted into more stable cyclic seleniranium cations. A key step is intramolecular which realized through anti-attack internal nucleophile, amidic nitrogen, to cation yielding intermediate imidazolinium Their deprotonation followed fused reaction products. Important transition states studied using density functional theory (DFT) methods. pathways investigated in detail. There two regioselective related 5-exo 6-endo Theoretical calculations monitoring (1)H NMR spectroscopy good agreement with consistent our experimental results. preferred pathway for products confirmed.
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doaj.org参考文章(46)
Marcello Tiecco, Electrophilic Selenium, Selenocyclizations ChemInform. ,vol. 31, pp. 7- 54 ,(2000) , 10.1007/3-540-48171-0_2
Sylvie Robin, Ge´rard Rousseau, Electrophilic cyclization of unsaturated amides Tetrahedron. ,vol. 54, pp. 13681- 13736 ,(1998) , 10.1016/S0040-4020(98)00698-X
Biljana M. Šmit, Radoslav Z. Pavlović, Three-step synthetic pathway to fused bicyclic hydantoins involving a selenocyclization step Tetrahedron. ,vol. 71, pp. 1101- 1108 ,(2015) , 10.1016/J.TET.2014.12.088
Nicolai Dieltiens, Diederica D. Claeys, Viktor V. Zhdankin, Victor N. Nemykin, Bart Allaert, Francis Verpoort, Christian V. Stevens, The pyroglutamate hydantoin rearrangement European Journal of Organic Chemistry. ,vol. 2006, pp. 2649- 2660 ,(2006) , 10.1002/EJOC.200600051
Congxiang Zha, George B. Brown, Wayne J. Brouillette, Synthesis and Structure−Activity Relationship Studies for Hydantoins and Analogues as Voltage-Gated Sodium Channel Ligands Journal of Medicinal Chemistry. ,vol. 47, pp. 6519- 6528 ,(2004) , 10.1021/JM040077O
Julie Charton, Sandrine Delarue, Sandrine Vendeville, Marie-Ange Debreu-Fontaine, Sophie Girault-Mizzi, Christian Sergheraert, Convenient synthesis of tetrahydroisoquinoline-hydantoins Tetrahedron Letters. ,vol. 42, pp. 7559- 7561 ,(2001) , 10.1016/S0040-4039(01)01526-X
Roger W. Alder, Fabrizio Carta, Christopher A. Reed, Irina Stoyanova, Christine L. Willis, Searching for intermediates in Prins cyclisations: the 2-oxa-5-adamantyl carbocation Organic and Biomolecular Chemistry. ,vol. 8, pp. 1551- 1559 ,(2010) , 10.1039/B921957A
Harald M. H. G. Albers, Loes J. D. Hendrickx, Rob J. P. van Tol, Jens Hausmann, Anastassis Perrakis, Huib Ovaa, Structure-Based Design of Novel Boronic Acid-Based Inhibitors of Autotaxin Journal of Medicinal Chemistry. ,vol. 54, pp. 4619- 4626 ,(2011) , 10.1021/JM200310Q
Thomas Bally, Paul R. Rablen, Quantum-Chemical Simulation of1H NMR Spectra. 2.† Comparison of DFT-Based Procedures for Computing Proton–Proton Coupling Constants in Organic Molecules The Journal of Organic Chemistry. ,vol. 76, pp. 4818- 4830 ,(2011) , 10.1021/JO200513Q
Aleksandr V. Marenich, Christopher J. Cramer, Donald G. Truhlar, Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. Journal of Physical Chemistry B. ,vol. 113, pp. 6378- 6396 ,(2009) , 10.1021/JP810292N