Substituent Control of Sigmatropic Periselectivity: Application to the Synthesis of (+/-)-Muscone

Article abstract of DOI:10.1021/jo00226a014

The thermal and anionic rearrangements of trans-1-vinylcyclotridec-3-en-1-ol compounds substituted in the α and β vinyl positions have been examined to determine whether the substituents can be used to control the periselectivity.For the anionic rearrangements, trimethylsilyl groups were found to be unsuitable, and terminal vinyl methyl or isopropyl groups did not provide a useful selectivity.Under thermal conditions, either a terminal trimethylsilyl or methyl gave high periselective control favoring the 1,3-shift siloxy Cope ring expansion relative to the 3,3-shift.This was used in a new synthesis of muscone.