Barluenga José, Diéguez Alejandro, Rodríguez Félix, Fañanás Francisco J, Sordo Tomás, Campomanes Pablo
Instituto Universitario de Química Organometálica, Enrique Moles, Unidad Asociada al CSIC, Universidad de Oviedo, Julián Clavería 8, 33006 Oviedo, Spain.
Chemistry. 2005 Sep 19;11(19):5735-41. doi: 10.1002/chem.200500537.
The [W(CO)5]-catalyzed cycloisomerization reaction of 1,1-disubstituted 4-pentyn-1-ol derivatives has been studied from both, an experimental and theoretical point of view. Three different catalytic systems have been evaluated {preformed [(thf)W(CO)5], [W(CO)6]/excess Et3N, and [W(CO)6]/2 mol % Et3N]. We have found that the reaction proceeds to give the formal endo- or exo-cycloisomerization products depending on the amount of Et3N used and on the substitution along the alkyl chain of the starting alkynol. The theoretical study allowed us to find the mechanisms of the reactions which explain the formation of the formal endo- or exo-cycloisomerization products.
已从实验和理论两个角度研究了[W(CO)₅]催化的1,1 - 二取代4 - 戊炔 - 1 - 醇衍生物的环异构化反应。评估了三种不同的催化体系{预制的[(thf)W(CO)₅]、[W(CO)₆]/过量Et₃N和[W(CO)₆]/2 mol% Et₃N}。我们发现，根据所用Et₃N的量以及起始炔醇烷基链上的取代情况，反应会生成形式上的内型或外型环异构化产物。理论研究使我们能够找到反应机理，这些机理解释了形式上的内型或外型环异构化产物的形成。
