Solvent-Assisted New Reaction Pathways for the (THF)W(CO)5-Promoted endo- and exo-Cycloisomerization of 4-Pentyn-1-ol: A Theoretical Investigation
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- 作者：Tomá ; s Sordo ; Pablo Campomanes ; Alejandro Dié ; guez ; Fé ; lix Rodrí ; guez ; and Francisco J. Fañ ; aná ; s
- 刊名：Journal of the American Chemical Society
- 出版年：2005
- 出版时间：January 26, 2005
- 年：2005
- 卷：127
- 期：3
- 页码：944 - 952
- 全文大小：515K
- 年卷期：v.127,no.3(January 26, 2005)
- ISSN：1520-5126
文摘
New solvent-assisted mechanistic routes were located for the (THF)W(CO)5-promoted endo-and exo-cycloisomerization of 4-pentyn-1-ol using the B3LYP/6-31G* (with the LANL2DZ relativisticpseudopotential for W) theory level. A mixed model was used by explicitly including a THF molecule as acomponent of the reactive system and taking into account the effect of bulk solvent by means of the PCM-UAHF method. This THF molecule plays a crucial role by making the endo route leading to the cycliccarbene complex the most favorable one because of an important catalytic effect. These new mechanismsallow a satisfactory rationalization of experimental facts.