Substituent effects in [3, 3]-sigmatropic rearrangements. Alkyl group effects and transition-state syn-diaxial interactions

CS Wilcox, RE Babston

文献索引：Wilcox,C.S.; Babston,R.E. Journal of the American Chemical Society, 1986 , vol. 108, p. 6636

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被引用次数: 29

摘要

Abstract: Rearrangement rates for nineteen Qallyl silylketene acetals {[(I-(allyloxy)-1-ethenyl) oxy] trialkylsilanes) are reported. Whereas rates for rearrangement of 1 and 2 exhibit a linear free energy relationship, no linear free energy relationship is observed between rates for 1 and 3. These data suggest the possibility of “syn-diaxial” interactions in a chair-like transition state for rearrangements of 3. The difference in free energy between 2 and 3 is found to be ...