利用鈀金屬催化腈基引導碳-氫鍵活化反應合成芴酮化合物

Pd-catalyzed synthesis of fluorenones via nitrile directed C-H bond activation

萬勇志(Yung-Chih Wan)

指導教授 ： 謝仁傑

淡江大學/理學院/化學學系碩士班/碩士(2013年)

https://doi.org/10.6846/TKU.2013.00882

摘要

我們成功利用鈀金屬/銀離子/三氟醋酸之混合系統，催化一系列2-腈基聯苯化合物進行碳氫鍵活化與腈基插入之級聯反應，同時，使用苯甲腈與碘苯做為起始物時，透過改變銀離子來源種類與其添加量，並延長反應時間，亦可成功得到欲求產物，利用此混合系統，可建構出具有廣泛取代基容忍度與良好產率的芴酮化合物。
於第三部分中，我們以2’-溴-[1,1’-聯苯]-2-甲腈做為起始物，使用格林納試劑與銅金屬催化下，成功地一步合成出菲啶化合物，而目前對於不同取代基容忍度的部分仍在進行中。

關鍵字

鈀金屬催化 ； 碳氫鍵活化 ； 芴酮

並列摘要

We are successfully in developing a composite system of [Pd]/[Ag]/TFA to catalyze cascade reactions of nitrile directed remote C–H bond activation with insertion of nitrile (part 1), meanwhile, as we change the starting materials from Biphenyl-2-carbonitriles to Benzonitriles and Iodobenzenes (part 2)
, the desired products could also be obtained by changing the species of the silver ions donor and it’s stoichiometric amount, through the using of this composite system, variously poly-substituted fluorenones were afforded in moderate to good yields with tolerance of a wide variety of substrates.
In third part, 2'-Bromo-[1,1'-biphenyl]-2-carbonitriles were as starting materials which were reacted with Grignard reagent and catalyzed by copper to synthesize phenanthridines in one-pot, further studies to explore the tolerance of the different substrates are currently underway.

並列關鍵字

Pd catalysis ； C-H bond activation ； Fluorenone

參考文獻

1. Tierney, M. T.; Grinstaff, M. W. J. Org. Chem. 2000, 65, 5355.

3. Oldridge, L.; Kastler, M.; M?ullen, K. Chem. Commun. 2006, 885.

4. (a) Chinnagolla, R. K.; M. Jeganmohan, M. Org. Lett. 2012, 14, 5246.

10. Campo, M. A.; Larock, R. C. J. Org. Chem. 2002, 67, 5616.

12. Thirunavukkarasu, V. S.; Parthasarathy, K.; Cheng, C.-H. Angew. Chem., Int. Ed. 2008, 47, 9462.