Concerted [4 + 2] and Stepwise (2 + 2) Cycloadditions of Tetrafluoroethylene with Butadiene: DFT and DLPNO-UCCSD(T) Explorations

Tetrafluoroethylene and butadiene form the 2 + 2 cycloadduct under kinetic control, but the Diels–Alder cycloadduct is formed under thermodynamic control. Borden and Getty showed that the preference for 2 + 2 cycloaddition is due to the necessity for syn-pyramidalization of the two CF2 groups in the...

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Bibliographic Details
Published in:Journal of organic chemistry 2020-03, Vol.85 (5), p.3858-3864
Main Authors: Svatunek, Dennis, Pemberton, Ryan P, Mackey, Joel L, Liu, Peng, Houk, K. N
Format: Article
Language:English
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Summary:Tetrafluoroethylene and butadiene form the 2 + 2 cycloadduct under kinetic control, but the Diels–Alder cycloadduct is formed under thermodynamic control. Borden and Getty showed that the preference for 2 + 2 cycloaddition is due to the necessity for syn-pyramidalization of the two CF2 groups in the 4 + 2 transition state. We have explored the full potential energy surface for the concerted and stepwise reactions of tetrafluoroethylene and butadiene with density functional theory, DFT (B3LYP and M06-2X), DLPNO-UCCSD­(T), and CASSCF-NEVPT2 methods and with the distortion/interaction–activation strain model to explain the energetics of different pathways. The 2 + 2 cycloadduct is formed by an anti-transition state followed by two rotations and a final bond formation transition state. Energetics are compared to the reaction of maleic anhydride and ethylene.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.0c00222