本文關(guān)鍵詞：有機(jī)小分子和酸介入的MBH反應(yīng)的研究　出處：《浙江大學(xué)》2017年博士論文　論文類(lèi)型：學(xué)位論文

  更多相關(guān)文章： MBH α β-不飽和酮 烯丙基化 domino反應(yīng) N-烷基化

【摘要】：碳-碳鍵的形成是有機(jī)化學(xué)中最基礎(chǔ)的反應(yīng)之一,在多個(gè)競(jìng)爭(zhēng)反應(yīng)位點(diǎn)選擇性地在特定位置上構(gòu)建碳-碳鍵是有機(jī)合成中非常具挑戰(zhàn)性的課題。Morita-Baylis-Hillman(MBH)反應(yīng)是一個(gè)非常重要的碳-碳鍵形成反應(yīng),可以廣泛地應(yīng)用于合成活性中間體以及精細(xì)化工產(chǎn)品。本論文主要研究了分子間α,β-不飽和酮與烯丙醇及其衍生物的烯丙基化反應(yīng),以及兩分子α,β-不飽和酮的domino關(guān)環(huán)反應(yīng)。第一章,簡(jiǎn)單介紹了MBH反應(yīng)的研究進(jìn)展,對(duì)MBH反應(yīng)三組分α,β-不飽和化合物、催化劑、親電試劑分別進(jìn)行了介紹,并重點(diǎn)介紹了親電試劑醛、亞胺、α,β-不飽和化合物、環(huán)氧化合物、芳基化合物、鹵代烴、烯丙基化合物等。第二章,膦與Br(?)nsted酸介入的分子間α,β-不飽和酮與烯丙基醋酸酯的MBH烯丙基化反應(yīng)。該反應(yīng)通過(guò)Pd(PPh_3)_4與P(n-Bu)_3共催化,AcOH作添加劑,能很好地得到α-烯丙基化產(chǎn)物。酸的加入,可有效抑制MBH插烯二聚副產(chǎn)物的生成。同時(shí),通過(guò)中間體的分離鑒別,我們提出了一個(gè)經(jīng)過(guò)穩(wěn)定鱗鹽中間體的可能機(jī)理。該反應(yīng)條件溫和,且具有很好的區(qū)域選擇性與E-立體選擇性。第三章,膦與Br(?)nsted酸介入的分子間α,β-不飽和酮與烯丙醇的MBH烯丙基化反應(yīng)。利用Pd(PPh_3)_4與P(n-Bu)_3共催化體系,在toluene/(CF_3)_2CHOH混合溶劑中,開(kāi)發(fā)出一種新穎的α,β-不飽和酮和烯丙醇的MBH反應(yīng)。并提出了利用(CF_3)_2CHOH生成鱗鹽和活化烯丙醇的可能機(jī)理。烯丙醇與烯丙基醋酸酯相比較,底物更加容易制備,且沒(méi)有額外的酯化步驟,烯丙醇作烯丙基化試劑副產(chǎn)物只有水,符合綠色化學(xué)與原子經(jīng)濟(jì)性的要求。該MBH反應(yīng)具有底物適用性廣、優(yōu)秀的區(qū)域選擇性和立體選擇性、較好的產(chǎn)率等諸多優(yōu)點(diǎn)。第四章,膦與Br(?)nsted酸介入的α,β-不飽和酮分子間MBH插烯反應(yīng)與Wittig串聯(lián)的domino關(guān)環(huán)反應(yīng)。該反應(yīng)在P(n-Bu)_3介導(dǎo)下,乙酸作添加劑,100℃反應(yīng)即可以良好的收率得到目標(biāo)產(chǎn)物。利用這種方法可以很好地得到β,γ-不飽和酮,酸的加入,可有效抑制MBH插烯二聚副產(chǎn)物的生成,同時(shí)也可以促使Wittig反應(yīng)的進(jìn)行。該反應(yīng)條件溫和,可耐受一系列官能團(tuán)。在論文的最后,我們也簡(jiǎn)單介紹了Lewis酸介入的N-烷基化反應(yīng)。以廉價(jià)的Lewis酸AlCl_3為催化劑,均三甲苯為反應(yīng)溶劑,100-176℃下反應(yīng)即可生成對(duì)應(yīng)的N-烷基化產(chǎn)物。該方法的優(yōu)點(diǎn)是底物適用性廣,脂肪族胺與芳香族胺、伯醇與仲醇都能有效地發(fā)生該反應(yīng),對(duì)胺的烷基化提供了一個(gè)新的參考方法。同時(shí),我們也對(duì)Lewis酸介入的N-烷基化反應(yīng)提出了一個(gè)合理的機(jī)理解釋。
[Abstract]:The formation of carbon-carbon bond is one of the most basic reactions in organic chemistry. The selective construction of carbon-carbon bonds at specific sites at multiple competitive reaction sites is a very challenging topic in organic synthesis. Morita-Baylis-Hillman (MBH). Reaction is a very important carbon-carbon bond formation reaction. It can be widely used in the synthesis of active intermediates and fine chemical products. In this paper, the allylation of 偽, 尾 -unsaturated ketones with allyl alcohols and their derivatives and the two molecules 偽 were studied. The domino ring closing reaction of 尾 -unsaturated ketones. Chapter 1, the research progress of MBH reaction is briefly introduced. The three components 偽, 尾 -unsaturated compounds and catalysts of MBH reaction are studied. The electrophilic reagents were introduced, and the electrophilic reagents, aldehydes, imines, 偽, 尾-unsaturated compounds, epoxy compounds, aryl compounds, halogenated hydrocarbons, allyl compounds, etc. Phosphine and Bran? The MBH allylation of 偽, 尾 -unsaturated ketones with allyl acetate was co-catalyzed by Pd(PPh_3)_4 and Pnsted. The 偽 -allylation product can be obtained by using AcOH as additive. The addition of acid can effectively inhibit the formation of dimeric by-product of MBH intercalation. At the same time, it can be identified by the separation and identification of intermediate. We have proposed a possible mechanism for the intermediate to stabilize the scale salt. The reaction conditions are mild and have good regioselectivity and E-stereoselectivity. The MBH allylation of allyl alcohol with 偽, 尾 -unsaturated ketones and allyl alcohols was studied. The co-catalytic system of Pd(PPh_3)_4 and Pnsted _ Bun _ (3) was used in the reaction of 偽, 尾 -unsaturated ketones with allyl alcohol. In the mixed solvent of toluene/(CF_3)_2CHOH, a novel 偽 was developed. The MBH reaction of 尾 -unsaturated ketones with allyl alcohols. A possible mechanism for the formation of scale salts and activation of allyl alcohols by using CF3CHOH was proposed. The comparison of allyl alcohols with allyl acetate was made. It is easier to prepare the substrate without additional esterification step. The byproduct of allyl alcohol as allylation reagent is only water, which meets the requirements of green chemistry and atomic economy. The MBH reaction has wide applicability of substrate. Excellent regioselectivity and stereoselectivity, good yield and many other advantages. Chapter 4th, phosphine and Brine? The intermolecular MBH intercalation reaction of 偽, 尾 -unsaturated ketones with Wittig was mediated by Pnsted acid mediated domino closure reaction. The target product can be obtained by the reaction of acetic acid as additive at 100 鈩，

本文編號(hào)：1405035