(a)含氟長鏈鈀錯合物在溫控系統與雙相系統中進行Sonogashira反應 (b)合成一系列陽離子型含氟鏈(η3-丙烯基)鈀錯合物及其結構與反應性之探討

(a) Pd Complexes with Fluorous-ponytailed for the Sonogashira Reaction under the Thermomorphic and Fluorous Biphasic System (b) Synthesis and Reactivity of Novel Cationic (η3-Allyl) Palladium Complexes Bearing Fluoro-ponytailed Bipyridine Ligands

陳怡權(Yi-Chuan Chen)

指導教授 ： 呂良賜

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2009年)

摘要

(a) 含氟長鏈鈀錯合物在溫控系統與雙相系統中進行Sonogashira反應

我們實驗室合成出的鈀錯合物[PdCl2(4,4’-bis-(RfCH2OCH2)-2,2’-bpy)](錯合物1a, Rf=C10F21)對於DMF具有溫控的特性。在此研究中，我們根據此特性，以芳香基碘化物及溴化物來與苯乙炔在DMF中以135±5℃下進行不含銅的Sonogashira反應，發現在溫控與FBS條件下皆可重複反應高達八次以上。而回收的觸媒以ICP-MS測定其回收率高達99.6%以上，而反應後的產物也利用管柱分離，並以GC-MS與1H NMR加以鑑定。

(b) 合成一系列陽離子型含氟鏈(η3-丙烯基)鈀錯合物及其反應性之探討

在這個研究中，我利用[Pd-(η3-丙烯基)Cl2]、AgOTf與我們一系列含氟鏈聯吡啶螯合劑[(4,4’-bis(RfCH2OCH2)-2,2’-bpy) Rf=C2F4H~C11F23]，在二氯甲烷下反應合成一系列含氟鏈(η3-丙烯基)鈀錯合物，再以NMR(1H，19F與13C)、FTIR、低解析質譜儀(LR-FAB)進行鑑定。將含較短氟鏈之錯合物利用再結晶的方式結出單晶，並送測X-ray單晶繞射儀解出其結構，接著嘗試催化進行氫胺化反應、偶氮反應與Suzuki耦合反應，並探討其反應性。

關鍵字

溫控系統 ； 氟有機雙向系統 ； Sonogashira耦合反應

並列摘要

(a) Pd Complexes with Fluorous-ponytails for the Sonogashira Reaction under the Thermomorphic and Fluorous Biphasic System

We synthesized Pd complexes [PdCl2(4,4’-bis-(RfCH2OCH2)-2,2’-bpy)] (complexes 1a, Rf=C10F21), and found the thermomorphic property in DMF. We then used aryliodide (arylbromide) as substrates to perform the Sonogashira cross-coupling reaction with phenylacetylene in DMF at 135±5℃. Under both thermomorphic and FBS conditions, the catalysts could be reused for eight runs. The recovery was about 99.66% as detected by ICP-Mass. Products have been separated by column chromatography, characterized by GC-Mass and 1H NMR.

(b) Synthesis and Reactivity of Novel Cationic (η3-Allyl) Palladium Complexes Bearing Fluoro-ponytailed Bipyridine Ligands

In this study, a series novel cationic (η3-Allyl) palladium complexes were synthesized by treating [Pd-(η3-allyl)Cl2] with the Fluoro-ponytailed bipyridine ligands and silver trifluoromethanesulfonate (AgOTf) in CH2Cl2. These complexes have been fully characterized by NMR (1H, 19F and 13C), FTIR, mass spectroscopy (FAB). Then we attempted the hydroamination, diazo coupling reaction, and the Suzuki reaction, with discussions on the reactivity.

並列關鍵字

thermomorphic system ； FBS ； sonogashira cross coupling reaction

參考文獻

[18] 陳世傑，含氟長鏈雙吡啶Pd金屬錯合物之Heck以及Suzuki反應研究，碩士論文，國立台北科技大學有機高分子所，台北，2008。

[1] J. Tsuji, H. Takahashi, M. Morikawa,Tetrahedron Lett. 1965, 4387

[2] C. Breutel, P. S. Pregosin, R. Salzmann, A. Togni, J. Am. Chem. Soc. 1994, 116, 4067

[8] A. Rezaeifard, M. Jafarpour, M. A. Naseri, R. Shariati, Dyes Pigm. 2008, 76, 840

[10] M. Kuriyama, R. Shimazawa, R. Shirai, Tetrahedron 2007, 63, 9393