Transition-Metal-Promoted Alkylations of Unsaturated Alcohols: The Ethylation of 3-Butyn-1-ol and 3-Buten-1-ol via Titanium Tetrachloride-Organoaluminum Ziegler-Natta Catalyst Systems

Article abstract of DOI:10.1021/jo00184a014

Reaction of 3-butyn-1-ol with diethylaluminum chloride followed by treatment with titanium tetrachloride under a variety of conditions gave selectively up to 70 percent yields of (E)-3-hexen-1-ol, the product expected from a syn ethylmetalation of the multiple bond.No complications arising from in situ β-hydride elimination were observed.Similarly, 4-pentyn-2-ol was ethylated to give (E)-4-hepten-1-ol; however, 3-pentyn-1-ol did not give an ethylated product.Additionally, the effect of "third components", i.e., Lewis bases, on the ethylation of 3-butyn-1-ol and 3-buten-1-ol was studied.