Thermolysis of unsymmetrically substituted vinylcyclopropanes. The effect of substituents on the site-selectivity of homo-[1,5]-sigmatropic hydrogen migrations

Abstract
Thermolysis of the unsymmetrical vinylcyclopropanes 18–24 reveals a notable substituent effect on the site-selectivity of homo-[1,5]-sigmatropic hydrogen shifts. Rearrangement of 18–20 (OMe substituent) produces only products 25–27, respectively (HA migration). In sharp contrast, thermolysis of 24 (Me3Si substituent) provides exclusively substance 34 (HX migration). Thermolysis of substrates bearing methyl (21, 22) or phenyl (23) groups provide, in each case, mixtures of the two possible products.

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