Abstract
Lanthanide triflate complexes of the type [Ln(OTf)~3~] (Ln=La, Sm, Nd, Yb, Lu) serve as effective, recyclable catalysts for the rapid intramolecular hydroalkoxylation (HO)/cyclization of primary/secondary and aliphatic/aromatic hydroxyalkenes in imidazolium‐based room‐temperature ionic liquids (RTILs) to yield the corresponding furan, pyran, spirobicyclic furan, spirobicyclic furan/pyran, benzofuran, and isochroman derivatives. Products are straightforwardly isolated from the catalytic solution, conversions exhibit Markovnikov regioselectivity, and turnover frequencies are as high as 47 h^−1^ at 120 °C. The ring‐size rate dependence of the primary alkenol cyclizations is 5>6, consistent with a sterically controlled transition state. The hydroalkoxylation/cyclization rates of terminal alkenols are slightly more rapid than those of internal alkenols, which suggests modest steric demands in the cyclic transition state. Cyclization rates of aryl‐functionalized hydroxyalkenes are more rapid than those of the linear alkenols, whereas five‐ and five/six‐membered spirobicyclic skeletons are also regioselectively closed. In cyclization of primary, sterically encumbered alkenols, turnover‐frequency dependence on metal‐ionic radius decreases by approximately 80‐fold on going from La^3+^ (1.160 Å) to Lu^3+^ (0.977 Å), presumably reflecting steric impediments along the reaction coordinate. The overall rate law for alkenol hydroalkoxylation/cyclization is v≈k[catalyst]^1^[alkenol]^1^. An observed ROH/ROD kinetic isotope effect of 2.48 (9) is suggestive of a catalytic pathway that involves kinetically significant intramolecular proton transfer. The present activation parameters—enthalpy (Δ__H__^≠^)=18.2 (9) kcal mol^−1^, entropy (Δ__S__^≠^)=−17.0 (1.4) eu, and energy (E~a~)=18.2 (8) kcal mol^−1^—suggest a highly organized transition state. Proton scavenging and coordinative probing results suggest that the lanthanide triflates are not simply precursors of free triflic acid. Based on the kinetic and mechanistic evidence, the proposed catalytic pathway invokes hydroxyl and olefin activation by the electron‐deficient Ln^3+^ center, and intramolecular H^+^ transfer, followed by alkoxide nucleophilic attack with ring closure.