Asymmetric Identity SN2 Transition States: Nucleophilic Substitution at alpfa-Substituted Carbon and Silicon Centers

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F62690094%3A18450%2F17%3A50005101" target="_blank" >RIV/62690094:18450/17:50005101 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1016/j.ijms.2016.06.003" target="_blank" >http://dx.doi.org/10.1016/j.ijms.2016.06.003</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1016/j.ijms.2016.06.003" target="_blank" >10.1016/j.ijms.2016.06.003</a>

Result language
angličtina
Original language name
Asymmetric Identity SN2 Transition States: Nucleophilic Substitution at alpfa-Substituted Carbon and Silicon Centers
Original language description
We have quantum chemically investigated the archetypal nucleophilic substitution reactions at carbon (SN2@C) and at silicon (SN2@Si) in the model reaction systems Cl– + A(CH3)2(CH2X)Cl (A = C, Si; X = H, F, Cl, Br, I) using relativistic density functional theory (DFT) at ZORAOLYP/ TZ2P. Our purpose is twofold. We wish to understand: (i) how the alpha-substituent X affects SN2 reactivity; and (ii) how methyl substituents at the central electrophilic atom A exactly participate in the transition vector of the Walden inversion. Interestingly, despite the fact that our SN2 model reactions are symmetric, i.e., constitute identity reactions, they proceed via slightly asymmetric transition states. We have also explored competing E2 pathways.
Czech name
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Czech description
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Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
30107 - Medicinal chemistry

Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year
2017
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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