σ,π-二金（I）炔配合物在烯炔反应中的作用
Role of σ,π-Digold(I) Alkyne Complexes in Reactions of Enynes.
作者信息
Ferrer Sofia, Echavarren Antonio M
机构信息
Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain.
Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, C/Marcel·li Domingo s/n, 43007 Tarragona, Spain.
出版信息
Organometallics. 2018 Mar 12;37(5):781-786. doi: 10.1021/acs.organomet.7b00668. Epub 2017 Dec 19.
Gold(I) acetylide and σ,π-digold(I) alkyne complexes derived from one prototypical 1,6-enyne and from 7-ethynyl-1,3,5-cycloheptatriene have been prepared and structurally characterized. Their possible role in gold(I)-catalyzed cycloisomerizations has been studied by experiment and by DFT calculations. Gold(I) acetylides are totally unproductive complexes in the absence of Brønsted acids. Similarly, no cyclizations were observed by heating σ,π-digold(I) alkyne digold(I) at least up to 130 °C. Theoretical studies provide a rationale for the much lower reactivity of digold species in reactions of enynes.
已制备并通过结构表征得到了源自一种典型的1,6-烯炔以及7-乙炔基-1,3,5-环庚三烯的金（I）乙炔化物和σ,π-二金（I）炔烃配合物。通过实验和密度泛函理论（DFT）计算研究了它们在金（I）催化的环异构化反应中可能发挥的作用。在没有布朗斯特酸的情况下，金（I）乙炔化物是完全没有活性的配合物。同样，将σ,π-二金（I）炔烃加热至至少130°C时，未观察到环化反应。理论研究为烯炔反应中双金物种反应活性低得多提供了一种解释。
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