Highly regio- and stereoselective cyclic iodoetherification of 4,5-alkadienols. An efficient preparation of 2-(1′(Z)-iodoalkenyl) tetrahydrofurans

Article abstract of DOI:10.1021/jo802079b

(Chemical Equation Presented) In this paper, an efficient way to synthesize 2-(1′(Z)-iodoalkenyl)tetrahydrofurans from 4,5-alkadienols and I ₂ was developed. The reaction of the 4,5-allenols with a substituent in the 3-position afforded the trans-2,3-disubstituted tetrahydrofurans with very high diastereoselectivity. However, when the axially optically active 4,5-allenol was treated with I₂ in n-hexane, the efficiency for chirality transfer was low. This problem was circumvented by conducting the reaction in CH₂Cl₂ at room temperature and applying N-iodosuccinimide as the electrophilic reagent; however, the Z/E ratio for the products is much lower. Highly optically active Z-products may be prepared via the kinetic resolution via a Sonogashira coupling reaction with propargyl alcohol.