Anti-hydroalumination of homo- and bishomopropargyl alcohols

Article abstract of DOI:10.1016/S0040-4039(97)00764-8

The reaction of ω-Me₃Si- or ω-Me₃Ge-substituted 3-butyn-1-ol, 4-pentyn-1-ol, and their derivatives with DIBAL-H and a small trialkylalane, e.g., Me₃Al or Et₃Al, at 23°C gives, after iodinolysis, the corresponding (Z)-4-iodo-3-buten-1-ols and (Z)-5-iodo-4-penten-1-ols in a highly stereo- and regio-selective manner, most probably via endo-dig mode cyclic anti-hydroalumination, while treatment of ω-carbosubstituted 3-butyn-1-ols with Red-Al or LialH₄ at high temperatures followed by iodinolysis can give the corresponding (Z)-4-iodo-3-buten-1-ols also in a highly regio- and stereoselective manner.