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Please use this identifier to cite or link to this item: http://ir.ncue.edu.tw/ir/handle/987654321/16889

Title: 重點ㄧ子題4:金屬促進水相加成反應:發展與應用(I)
Metal-Mediated Addition Reactions in Aqueous Media: Development and Application (I)
Authors: 林美惠
Contributors: 化學系
Keywords: 水相羥甲基化反應;市售甲醛水溶液;烯丙基化反應
Date: 2010
Issue Date: 2013-06-06T02:34:23Z
Publisher: 行政院國家科學委員會
Abstract: 帶有手性中心的丁烯醇(2)是有機合成上重要的合成單體, 其傳統合成方法是由帶有手性中心的3-羥基2-甲基丙酸甲酯經多步驟合成而來(式2,3)。 目前我們使用市售甲醛水溶液為反應試劑, 與溴化物(1)和銦金屬進行烯丙基化反應,成功得到丁烯醇(2) (式1)。 本研究計畫提出新合成策略, 發展不對稱水相羥甲基化反應, 而反應產物丁烯醇(2)產生新的手性中心, 是取決於烯丙基的反應位向, 此為新穎不對稱合成技術。 以此不對稱合成技術能精簡合成步驟, 更能有效合成帶有手性中心的丁烯醇。除了進行烯丙基化反應, 我們也企圖發展苯甲基化反應(benzylation), 可應用在合成帶有手性中心的苯丙酸。 帶有手性中心的苯丙酸像Naproxen, Ibuprofen 為非類固醇性抗炎藥,用於治骨關節炎和類風濕性關節炎。我們也成功發展以純水為溶劑,利用金屬錫與二氫呋喃(3a)、二氫哌喃(3b)進行烯丙基化反應 (式4)。 此反應不止僅限於二氫呋喃和二氫哌喃,見式5。 本研究計畫將探討利用金屬錫進行水相加成反應,可望應用到含氮醣(azasugar)的合成。
Chiral functionalized homoallylic alcohol 2 is a useful building block in organic synthesis. Isoprene is a C5 unit found in many natural products, and the synthetic application of homoallylic alcohol 2 is reported in the synthesis of terpenoid hydrocarbons, macrolides and polyether antibiotics. The general synthetic route to access homoallylic alcohol 2 is from methyl 3-hydroxy-2-methylpropionate (eq 2, 3). The metal-mediated Barbier-type allylation of formaldehyde would provide a facile route to the homoallylic alcohol 2. As the source of formaldehyde, the use of a commercial formaldehyde aqueous solution is the most convenient. Herein, an aqueous hydroxymethylation of γ-substituted allyl halides 1 was developed in our group (eq 1). The formaldehyde addition reaction in an asymmetric version was proposed. The benzylation of formaldehyde remains a synthetic insolubility so far. Our attempts in this arena were also described in the proposal. In addition, a new tin-mediated allylation of dihydrofuran (3a) and dihydropyran (3b) to the corresponding 1,4- or 1,5-diols was developed in our group (eq 4). This method was not only applicable on dihydropyrans and dihydrofurans but also methyl 3-methoxyacrylate (eq 5). The scope of tin-mediated allylation would be studied.
Relation: 國科會計畫, 計畫編號: NSC99-2119-M018-001; 研究期間: 9908-10007
Appears in Collections:[化學系] 國科會計畫

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