噻吩并[3,4-c]吡咯-4, 6-二酮(TPD)之鈀催化直接碳氫鍵芳香環化反應之研究: 以高步驟經濟效益合成策略製備含TPD之功能性π-共軛小分子

Pd-Catalyzed Direct C-H Arylation of Thieno[3,4-c]pyrrole- 4,6-dione (TPD): A Step-Economical Synthetic Alternative to Access Symmetrical π-Conjugated Functional Molecules

張善芸(Shan-Yun Chang)

指導教授 ： 劉青原

國立中央大學/工學院/化學工程與材料工程學系/碩士(2014年)

摘要

以thieno[3,4-c]pyrrole-4,6-dione (TPD)為核心作分子共軛延伸的結構已在光電元件上被廣泛研究，在本論文中，探討以鈀催化直接碳氫鍵活化之方法取代傳統的交叉耦合反應來製備含TPD單元的π共軛功能性小分子。碳氫鍵活化的方法不僅具有步驟經濟性、原子經濟性、減少副產物產生，成本低於傳統的交叉耦合反應，故鈀催化之直接碳氫鍵活化之合成方法已逐漸取代傳統交叉耦合反應。

本研究一開始以TPD與溴苯為反應物，嘗試不同的催化劑、配位基、鹼、溶劑，以找到最佳化條件，其中，我們發現溶劑的極性對於反應的轉換率具有決定性的影響。利用找到的最佳化條件，TPD或其衍生物與具有各種不同官能基的芳香基溴化物可順利地進行鈀催化碳氫鍵活化的反應。此反應中對於官能基容忍性非常好，像是酯基、腈基、酮基、醛基還有含鹵素基都是可以被容忍的。

關鍵字

噻吩并[3,4-c]吡咯-4, 6-二酮 ； 鈀催化直接碳氫鍵芳香環化反應 ； 高步驟經濟效益 ； 功能性π-共軛小分子

並列摘要

We demonstrate a step-economical and viable synthetic alternative to access a series of thieno[3,4-c]pyrrole-4,6-dione (TPD)-based π-conjugated molecules through Pd-catalyzed direct C-H arylations. A comprehensive synthetic study including the screening of various kinds of palladium catalysts, ligands, and bases is reported. Under the optimum reaction conditions, TPD and its common derivatives underwent efficient and mild direct C-H arylations with a variety of functionalized bromoarenes. Functional groups such as ester, nitrile, ketone, aldehyde, and halide were well-tolerated, which substantially extended the reaction scope. We wish the reported method would provide materials scientists a relatively greener synthetic route to efficiently prepare the TPD-containing π-functional materials.

並列關鍵字

Thieno[3,4-c]pyrrole- 4,6-dione ； Pd-Catalyzed Direct C-H Arylation ； Step-Economical ； π-Conjugated Functional Molecules

參考文獻

[1] D. J. Schipper and K. Fagnou, “ Direct Arylation as a Synthetic Tool for the Synthesis of Thiophene-Based Organic Electronic Materials ”, Chem. Mater., Vol 23, pp. 1594-1600, March 2011.

[2] W. Li, C. Du, F. Li, Y. Zhou, M. Fahlman, Z. Bo and F. Zhang, “ Benzothiadiazole-Based Linear and Star Molecules: Design, Synthesis, and Their Application in Bulk Heterojunction Organic Solar Cells ”, Chem. Mater., Vol 21, pp. 5327-5334, November 2009.

[3] A. Facchetti, M.-H. Yoon, C. L. Stern, H. E. Katz, T. J. Marks, “Building Blocks for n-Type Organic Electronics: Regiochemically Modulated Inversion of Majority Carrier Sign in Perfluoroarene-Modified Polythiophene Semiconductors”, Angew. Chem. Int. Ed., Vol 42, pp. 3900-3903, August 2003.

[5] T. Satoh, Y. Kawamura, M. Miura and M. Nomura, “ Palladium-Catalyzed Regioselective Mono- and Diarylation Reactions of 2-Phenylphenols and

[6] L. Ackermann, S. Barfüßer, “ Palladium-Catalyzed Direct C-3 Arylations of Indoles with an Air-Stable HASPO ”, Synlett., Vol 2009, pp. 808 – 812, March 2009.