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National Chung Hsing University Institutional Repository - NCHUIR > 理學院 > 化學系所 > 依資料類型分類 > 碩博士論文 >  1.利用碳-氫鍵活化的策略合成高位置選擇性的芳香基硫屬化合物 2.水相銅催化醛類與硫醇生成硫酯之交互耦合反應

Please use this identifier to cite or link to this item: http://nchuir.lib.nchu.edu.tw/handle/309270000/151781

標題: 1.利用碳-氫鍵活化的策略合成高位置選擇性的芳香基硫屬化合物 2.水相銅催化醛類與硫醇生成硫酯之交互耦合反應
1.Regioselective synthesis of aryl chalcogenides through C-H Activation 2.Copper-catalyzed coupling reaction of aldehydes with thiols in water
作者: 易志倫
Yi, Chih-Lun
Contributors: 李進發
Chin-Fa Lee
化學系所
關鍵字: 碳氫鍵活化;硫屬化合物;水相;銅催化;;硫酯;耦合反應
C-H Activation;Copper-catalyzed;aldehydes;thioester
日期: 2013
Issue Date: 2013-11-07 12:56:49 (UTC+8)
Publisher: 化學系所
摘要: 利用已知的銥金屬做為催化劑使1,3雙取代芳香環上的碳-氫鍵形成碳-硼鍵,再利用氯化亞銅和配體的幫助下,催化碳-硒或碳-碲鍵的生成,得到3,5雙取代硒醚或碲醚,這是首次在一鍋化反應中直接生成間位取代硒醚或碲醚化合物。然而烷基硫醇在此系統中的反應性並不理想。值得鼓舞的是經過銥金屬和配體的催化活化1,3雙取代芳香環上間位的碳-氫鍵形成碳-硼鍵,接著在醋酸銅以及吡啶的幫助下,進行碳-硫及碳-硒鍵的生成,得到高位置選擇性的硫醚及硒醚化合物。此外,官能基的容忍性也非常廣泛,無論是推電子基團、拉電子基團或含氮雜環皆可以適用在此反應條件。更重要的是,不僅芳香基硫醇和芳香基二硒化合物可作為耦合的反應物之外,烷基硫醇和烷基二硒化合物皆可以得到相對應的產物。
我們發展一個簡便的方法合成硫酯化合物,利用銅金屬催化醛類與硫醇通過以過氧化叔丁醇作為氧化劑下進行碳-硫鍵的生成。官能基包含了氯基、三氟甲基、溴基、碘基、腈基、酯基和噻吩都可以容忍在此反應條件。更重要的是,此反應是以水當做溶劑並且不需要加入任何的相轉移試劑。
The direct meta C-H functionalization of C-H bond of aromatic ring is introduced. The combination of iridium-Catalyzed C-H activation and sequential functionalization of the resulting aryl boronic ester is an excellent approach for regioselection meta C-H functionalization of aromatic C-H bond. However, alkyl disulfides were not suitable as the coupling partners in this system. To our delight, the combination of Cu(OAc)2 and pyridine could be applied to promote the C-S and C-Se bond formations. Thus, the aryl alkyl thioethers and selenides could be prepared through sequential iridium-catalyzed meta C-H borylation and copper-promoted C-S and C-Se bond formations in one pot.
A general procedure for the syntheses of aryl thioethers and aryl selenides in one-pot through the sequential iridium-catalyzed meta C-H borylation and copper-promoted C-S and C-Se bond formations in one-pot is described. Functional groups including chloro, nitro, fluoro, trifluoromethyl and nitrogen-containing heterocycles are all tolerated by the described reaction conditions. Importantly, not only aryl thiols and selenides but also alkyl analogs are all suitable coupling partners, giving the products with high meta-regioselectivity and good yields.
A copper-catalyzed C-S bond formation between aldehydes and thiols in the presence of TBHP as an oxidant is described. Functional groups including chloro, trifluoromethyl, bromo, iodo, nitrile, ester and thiophene are all tolerated by the reaction conditions employed. Importantly, this reaction is performed in water without the use of a surfactant.
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