Dérien Sylvie, Ropartz Loïc, Le Paih Jacques, Dixneuf Pierre H.
UMR 6509, CNRS-Université de Rennes, Organométalliques et Catalyse, Campus de Beaulieu, F-35042 Rennes, France.
J Org Chem. 1999 May 14;64(10):3524-3531. doi: 10.1021/jo982300t.
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.
在钌（II）催化剂RuCl（cod）（C（5）Me（5））存在的情况下，实现了丙-2-炔-1-醇与烯丙醇的碳-碳偶联。该偶联反应具有高度的区域选择性，在室温或80℃下分别生成HOCR（2）C（=CH（2））CH（2）CH（2）CHO异构体，环化后生成2-羟基-或2-烷氧基-5-亚甲基四氢吡喃。它用于合成含有两个和三个四氢吡喃部分的分子。对多种丙-2-炔-1-醇的研究表明，炔丙基碳上的取代基对碳-碳偶联的区域选择性有影响。对于叔醇，反应仅生成一种环状异构体，即2-烷氧基四氢吡喃，而对于仲醇，还会得到一种线性异构体。四氢吡喃醇很容易被氧化成内酯。
