Reactions of Epoxides with 3,3,4,4-Tetraethoxybut-1-yne Acetylide: Selective Formation of Propargylic and Homopropargylic Alcohols

Abstract

3,3,4,4-Tetraethoxybut-1-yne acetylide (TEB^–) reacted with several epoxides under a variety of conditions. When the acetylide counterion was lithium, nothing happened in the absence of ammonia and HMPA, but reaction of TEBLi with a mixture of oxirane and BF₃ (oxirane/BF₃ addition to the acetylide) followed by hydrolysis gave the expected homopropargylic alcohols in about 80% yield. When the counterion was MgBr⁺, oxirane-to-aldehyde rearrangement took place before the acetylide reacted and gave propargylic alcohols in good yields in all cases except one; the only exception was ethylene oxide, which gave the homopropargylic alcohol in 70% yield.

Key words

epoxides - acetylides - counterions - oxirane rearrangement - homopropargylic alcohol - propargylic alcohols

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