Timothy Ramadhar - Resolving the Mechanistic Origins of E/Z-Selectivity Differences for the ortho-Aryl-Claisen [3,3]-Sigmatropic Rearrangement through DFT Calculations

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      Publication Details (including relevant citation   information):

      Timothy R. Ramadhar, Robert A. Batey. Computational and   Theoretical Chemistry, 2011, 974.   76-78.

      Abstract:

      The mechanistic origins of E/Z-product   selectivity differences for the synthetically important thermal   ortho-aryl-Claisen [3,3]-sigmatropic rearrangement is   resolved through a computational study. The formation of   E- and Z-products has previously been proposed   to occur as a result of reaction via different chair-like   transition states or through chair- and boat-like transition   states. Using DFT B3LYP/6-31G* calculations on a previously   reported experimental system, it has been determined that   differences in E/Z-product selectivities   primarily arise by progression through different chair-like   transition states.

      Address (URL): http://dx.doi.org/10.1016/j.comptc.2011.07.018