Bifurcating reactions: distribution of products from energy distribution in a shared reactive mode
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F21%3A00545403" target="_blank" >RIV/61388955:_____/21:00545403 - isvavai.cz</a>
Result on the web
<a href="http://hdl.handle.net/11104/0322099" target="_blank" >http://hdl.handle.net/11104/0322099</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d1sc02826j" target="_blank" >10.1039/d1sc02826j</a>
Alternative languages
Result language
angličtina
Original language name
Bifurcating reactions: distribution of products from energy distribution in a shared reactive mode
Original language description
Bifurcating reactions yield two different products emerging from one single transition state and are therefore archetypal examples of reactions that cannot be described within the framework of the traditional Eyring's transition state theory (TST). With the growing number and importance of these reactions in organic and biosynthetic chemistry, there is also an increasing demand for a theoretical tool that would allow for the accurate quantification of reaction outcome at low cost. Here, we introduce such an approach that fulfils these criteria, by evaluating bifurcation selectivity through the energy distribution within the reactive mode of the key transition state. The presented method yields an excellent agreement with experimentally reported product ratios and predicts the correct selectivity for 89% of nearly 50 various cases, covering pericyclic reactions, rearrangements, fragmentations and metal-catalyzed processes as well as a series of trifurcating reactions. With 71% of product ratios determined within the error of less than 20%, we also found that the methodology outperforms three other tested protocols introduced recently in the literature. Given its predictive power, the procedure makes reaction design feasible even in the presence of complex non-TST chemical steps.
Czech name
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Czech description
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Classification
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
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA21-10383S" target="_blank" >GA21-10383S: Control of Reaction Selectivity by Asynchronicity</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2021
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Chemical Science
ISSN
2041-6520
e-ISSN
2041-6539
Volume of the periodical
12
Issue of the periodical within the volume
38
Country of publishing house
GB - UNITED KINGDOM
Number of pages
13
Pages from-to
12682-12694
UT code for WoS article
000691879500001
EID of the result in the Scopus database
2-s2.0-85116894431