Double Mitsunobu Reactions of cis-Cycloalk-2-ene-1,4-diols and 3,4-Epoxycycloalkenes: Rearrangements of Allylic Diazides

Abstract

Double Mitsunobu reactions of cis-cycloalk-2-ene-1,4-diols and 3,4-epoxycloalkenes were investigated. cis-3,5-Diazidocyclopentene, cis-3,4-diazidocyclooctene, and cis-3,8-diazidocyclooctene were formed as sole products via the Mitsunobu reaction. cis-Cyclohex-2-ene-1,4-diol, 3,4-epoxycyclohexene and trans-2-azidocyclohex-3-en-1-ol gave a mixture of cis-3,6-diazidocyclohexene and cis-3,4-diazidocyclohexene via a sigmatropic rearrangement. In the same manner, cis-cyclohept-2-ene-1,4-diol, 3,4-epoxycycloheptene and trans-2-azidocyclohept-3-en-1-ol gave a mixture of cis-3,7-diazidocycloheptene and cis-3,4-diazidocycloheptene. Experimental results were explained by theoretical PM3 calculations.

Key Words

allylic diazides - Mitsunobu reaction - sigmatropic rearrangement

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