Efficient Intramolecular Hydroalkoxylation of Unactivated Alkenols Mediated by Recyclable Lanthanide Triflate Ionic Liquids: Scope and Mechanism

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 degrees 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 A) to Lu(3+) (0.977 A), presumably reflecting steric impediments along the reaction coordinate. The overall rate law for alkenol hydroalkoxylation/cyclization is v approximately 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 (DeltaH(++))=18.2 (9) kcal mol(-1), entropy (DeltaS(++))=-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.

Catalytic, Enantioselective, Intramolecular Sulfenofunctionalization of Alkenes with Phenols

“…18 Methanesulfonic acid and ethanesulfonic acid were dried as described in the literature. 22 Substrates 2-(( E )-3-thiophene-ylprop-2-en-1-yl)phenol ( 3k ), 40 2-(but-3-en-1-yl)phenol ( 3p ) 41 and 2-(pent-4-en-1-yl)phenol ( 3q ) 42 were prepared as described. Intermediates ( E )-3-(furan-2-yl)-1-(2-hydroxyphenyl)prop-2-en-1-one ( S2 ) 43 and diethyl ( E )-2-(5-(2-hydroxyphenyl)pent-2-en-1-yl)malonate ( S3 ) 44 were prepared as described.…”

Migratory Insertion of Alkenes into Metal–Oxygen and Metal–Nitrogen Bonds

“…Although lanthanide-catalyzed cyclizations of alkenyl alcohols have been reported, these reactions do not proceed through a pathway involving migratory insertion of the alkene into an LnÀO bond. [48] The thermodynamics of the insertion of an alkyne and a terminal alkene into LnÀO bonds have been examined by calorimetry and these data predict that the insertion of an alkyne is exothermic (DH = À13 kcal mol À1 ), but the insertion of a terminal alkene is significantly endothermic (DH = + 22 kcal mol À1 ). [49] Reactions [50] The reaction is first order in platinum methoxide and tetrafluoroethylene.…”

Iridium-Catalyzed, Intermolecular Hydroetherification of Unactivated Aliphatic Alkenes with Phenols

“…Although lanthanide-catalyzed cyclizations of alkenyl alcohols have been reported, these reactions do not proceed through a pathway involving migratory insertion of the alkene into an LnÀO bond. [48] The thermodynamics of the insertion of an alkyne and a terminal alkene into LnÀO bonds have been examined by calorimetry and these data predict that the insertion of an alkyne is exothermic (DH = À13 kcal mol À1 ), but the insertion of a terminal alkene is significantly endothermic (DH = + 22 kcal mol À1 ). [49] Reactions of Metal Alkoxo Complexes with Alkenes for which Direct Evidence has been Gained for Migratory Insertion into an M À O Bond Although analysis of catalytic olefin alkoxylation systems provided stereochemical and kinetic evidence for a synoxypalladation step by migratory insertion of an alkene ligand into a M À O bond, the metal alkoxo complexes that were predicted to insert olefins have not been isolated and fully characterized.…”