Synthesis of 2-Alkoxy-5-methylenetetrahydropyrans: A Regioselective Ruthenium-Catalyzed C-C Coupling Reaction of Prop-2-yn-1-ols with Allyl Alcohol.
The carbon-carbon coupling of prop-2-yn-1-ols with allyl alcohol is achieved in the presence of the ruthenium(II) catalyst RuCl(cod)(C(5)Me(5)). The coupling reaction is highly regioselective and leads to the HOCR(2)C(=CH(2))CH(2)CH(2)CHO isomer and, after cyclization, to either 2-hydroxy- or 2-alkoxy-5-methylenetetrahydropyrans, at room temperature or at 80 degrees C, respectively. It is used for the synthesis of molecules containing two and three tetrahydropyran moieties. The study of a variety of prop-2-yn-1-ols has shown the influence of the substituent at the propargyl carbon on the regioselectivity of the C-C coupling. In the case of tertiary alcohols, the reaction leads to only one cyclic isomer, the 2-alkoxytetrahydropyran whereas with secondary alcohols, a linear isomer is also obtained. The tetrahydropyranols are easily oxidized into lactones.
Dérien
Sylvie
S
UMR 6509, CNRS-Université de Rennes, Organométalliques et Catalyse, Campus de Beaulieu, F-35042 Rennes, France.
Ropartz
Loïc
L
Le Paih
Jacques
J
Dixneuf
Pierre H.
PH