Institute for Organic and Analytical Chemistry/MAPEX Center for, Materials and Processes, University of Bremen, Leobener Str. 7/ Bibliothekstr. 1, 28359, Bremen, Germany.
Institute for Inorganic Chemistry and Crystallography/, MAPEX Center for Materials and Processes, University of Bremen, Leobener Str. 7/Bibliothekstr. 1, 28359, Bremen, Germany.
Chemistry. 2019 Oct 17;25(58):13318-13328. doi: 10.1002/chem.201902255. Epub 2019 Sep 4.
Zirconacyclopentadienes are versatile precursors for a large number of heteroles, which are accessible by Zr-element exchange reactions. The vast majority of reports describe their preparation by the use of Negishi's reagent, which is a species that is formed in situ. The zirconacyclopentadiene is then formed by the addition of one equivalent of a diyne or two equivalents of a monoyne moiety to this Negishi species. Another route involves Rosenthal's reagent (Cp Zr(py)Me SiC≡CSiMe ), which then reacts with a diyne or monoyne moiety. In this work, the efficiency of both routes was compared in terms of reaction time, stability of the product in the reaction mixture, and yield. The synthetic implications of using both routes are evaluated. Novel zirconacyclopentadienes were synthesized, characterized directly from the reaction mixture, and crystal structures could be obtained in most cases.
茂金属环戊二烯基锆是许多杂环化合物的多功能前体，可通过 Zr 元素交换反应获得。绝大多数报道都描述了通过使用 Negishi 试剂制备茂金属环戊二烯基锆，这是一种原位形成的物质。然后，通过向该 Negishi 物种中添加一当量的二炔或两当量的单炔部分，形成茂金属环戊二烯基锆。另一种途径涉及 Rosenthal 试剂（CpZr(py)MeSiC≡CSiMe3），然后与二炔或单炔部分反应。在这项工作中，从反应时间、反应混合物中产物的稳定性和产率等方面比较了这两种途径的效率。评估了使用这两种途径的合成意义。直接从反应混合物中合成了新型茂金属环戊二烯基锆，并在大多数情况下获得了晶体结构。
