Title

Cations or Radicals? Inherent Reactivity of Biosynthetic Intermediates in the B-Ring Formation of Rotenoid Natural Products

Abstract

Compounds of the rotenoid class are naturally occurring in the Leguminosae and Nyctaginacae families. Rotenoids have found a myriad of uses, for example, in the agricultural industry as an insecticide and piscicide, and as an anticancer therapeutic. The scientific literature questions whether cyclization of the rotenoid B-ring occurs via a pathway containing either cationic or free-radical intermediates. In this work, both propositions are analyzed using DFT (B3LYP and M06-2X) and the G3 composite method in gas- and (implicit) solution-phase. The accuracy of these methods is compared to several experimental C-H bond dissociation energies (BDEs). We find that of the methods surveyed M06-2X provides the most accurate BDEs. Further, there is a clear thermodynamic preference for the free-radical pathway.

Department(s)

Chemistry

Document Type

Article

DOI

https://doi.org/10.1021/acs.jpca.5b12367

Keywords

cyclization, bond cleavage, oxygen, solvents, crystal cleavage

Publication Date

2016

Recommended Citation

Kirkpatrick, Adam K., and Matthew R. Siebert. "Cations or Radicals? Inherent Reactivity of Biosynthetic Intermediates in the B-Ring Formation of Rotenoid Natural Products." The Journal of Physical Chemistry A 120, no. 15 (2016): 2372-2379.

Journal Title

The Journal of Physical Chemistry A

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