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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Experimental and Theoretical Investigation of the Synchronicity of Ambident Silyloxypyrone-Based (5 + 2)
Adam J Youman1, Samantha N Rokey1, Jacob P Grabowski1
1Department of Chemistry, Illinois State University, Campus Box 4160, Normal, Illinois 61790-4160, United States.
Abstract:
The reaction pathway of silyloxypyrone-based (5 + 2) cycloadditions was determined to be extremely dependent on the nature of the dipolarophile. Neutral alkenes were the least reactive, whereas both electron-deficient and electron-rich dipolarophiles were more reactive, thus providing evidence for ambident oxidopyrylium intermediates. Qualitative rate studies, Hammett linear free energy relationships, and theoretical calculations combined to provide evidence for a spectrum of reactivity that passes through the borderlands of concerted and stepwise.
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