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Kellie L Tuck - One of the best experts on this subject based on the ideXlab platform.

David P G Hamon - One of the best experts on this subject based on the ideXlab platform.

Tuck, Kellie Louise - One of the best experts on this subject based on the ideXlab platform.

Kleczka Margarethe - One of the best experts on this subject based on the ideXlab platform.

  • Strong Asymmetry in the Perepoxide Bifurcation Mechanism: The Large-Group Effect in the Singlet Oxygen Ene Reaction with Allylic Alcohols
    'Wiley', 2017
    Co-Authors: Griesbeck, Axel G., Goldfuss Bernd, Jaeger Christina, Bruellingen Eric, Lippold Tim, Kleczka Margarethe
    Abstract:

    The singlet oxygen reactions of sterically crowded Allylic Alcohols result in the preferential formation of g-hydroperoxy Alcohols with regioselectivities up to 98:2. The kinetic cis effect still prevails in the first, rate-determining step of this two-step non-intermediate ene mechanism (k(E-5)/k(Z-5)=1.9). The Primary Allylic Alcohol 3 showed no regioselectivity at all, increasing the steric demands at the a carbon and directing the singlet oxygen addition towards the gamma carbon up to 98:2 regioselectivity. DFT calculations rationalized these results and show the decisive role of the symmetry-breaking bifurcation following the early transition states. The use of the products as substrates for the synthesis of five-and seven-membered ring peroxides, namely 4-methylene-1,2-dioxolanes and 6-methylene-1,2,4-trioxepanes, by rare earth metal complexes as Lewis acids is also demonstrated

Hamon, David P. G. - One of the best experts on this subject based on the ideXlab platform.