Bifurcating reactions: distribution of products from energy distribution in a shared reactive mode

0545403 - ÚFCH JH 2022 RIV GB eng J - Journal Article
Bharadwaz, Priyam - Maldonado-Domínguez, Mauricio - Srnec, Martin
Bifurcating reactions: distribution of products from energy distribution in a shared reactive mode.
Chemical Science. Roč. 12, č. 38 (2021), s. 12682-12694. ISSN 2041-6520. E-ISSN 2041-6539
R&D Projects: GA ČR(CZ) GA21-10383S
Grant - others:Ministerstvo školství, mládeže a tělovýchovy - GA MŠk(CZ) LM2018140
Institutional support: RVO:61388955
Keywords : initio molecular-dynamics * possible path bifurcation * diels-alder * transition-state * nonstatistical dynamics * pericyclic-reactions * 4+2 cycloadditions * basis-sets * mechanism * selectivity
OECD category: Physical chemistry
Impact factor: 9.969, year: 2021
Method of publishing: Open access

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.
Permanent Link: http://hdl.handle.net/11104/0322099