1,5-Shift of unsaturated groups; migratory aptitudes of substituted vinyl groups and evidence for exo-selectivity

Abstract
For the 1,5-sigmatropic shift converting (1; X =E-substituent) into (2), migratory aptitude correlates with the resonance electron-accepting ability of the substituent X; Z-olefins migrate faster than their E-isomers, and (6) racemises faster than (7) in accord with migration via an exo-arrangement (4) rather than an endo-arrangement (5).

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