本文選題：軸手性聯(lián)芳烴類 + BINAM�。� 參考：《第四軍醫(yī)大學(xué)》2014年碩士論文

【摘要】：1,1’-binaphthyl-2,2,-diamine(BINAM)衍生物是非常有用的手性聯(lián)芳烴類化合物，和幾個(gè)以BINAM為基礎(chǔ)的催化劑已經(jīng)用于不對(duì)稱催化。然而，缺少合適的合成方法阻礙了它們的發(fā)展。立體選擇性的合成BINAM的方法很少，BINAM的合成主要依賴于傳統(tǒng)的合成方法，雖然有些立體選擇的氧化耦合的報(bào)道。與BINOL不同，氧化耦合方法并不十分有效。酸催化二芳基肼[3,3]-重排可能是一個(gè)合成外消旋或光學(xué)活性的BINAM衍生物的有效的和通用的方法。最近，Kürti和List小組使用手性磷酸酸催化二芳基肼[3,3]-重排合成光活性的聯(lián)萘胺。不幸的是，這種方法從實(shí)際來看，二芳基肼和手性磷酸酸的合成十分困難。立體選擇,方便和有效的合成結(jié)構(gòu)多樣化BINAM衍生物將對(duì)于發(fā)現(xiàn)新的聯(lián)芳烴類手性配體和催化劑有深遠(yuǎn)的影響。本論文研究工作描述一個(gè)有效和實(shí)用的合成光活性BINAM衍生物的[3,3]-重排的方法。 1.使用金屬催化鹵代芳烴與胺類化合物的交叉偶聯(lián)，用于合成薄荷氧羰基保護(hù)的二芳基肼，篩選了不同配體和金屬的組合，反應(yīng)溫度，反應(yīng)時(shí)間和溶劑等，來得到最佳的反應(yīng)條件，使得產(chǎn)率最高。 2.在N,N'-雙(2-萘基)-肼基甲酸-(-)-薄荷酯等發(fā)生分子內(nèi)重排反應(yīng)的反應(yīng)中，我們篩選了不同的酸、溶劑、反應(yīng)溫度和反應(yīng)時(shí)間等，確定了最佳的反應(yīng)條件，使得雜質(zhì)最少，，產(chǎn)率最高。 3.探索了52a等化合物酰胺鍵的水解條件，分別使用酸水解和堿水解兩種方式可以得到產(chǎn)物聯(lián)萘胺及其衍生物，酸水解得到的產(chǎn)物中有雜質(zhì)生成，而堿水解基本定量反應(yīng)，產(chǎn)率很高。使用HPLC檢測(cè)所得產(chǎn)物ee值都在99%以上。 本論文設(shè)計(jì)合成了光學(xué)活性的聯(lián)萘胺及其衍生物，為手性聯(lián)萘胺及其衍生物的合成提供了一條可行有效的合成途徑，為手性聯(lián)萘胺的進(jìn)一步應(yīng)用打下了基礎(chǔ)。
[Abstract]:However, their development is hampered by the lack of suitable synthetic methods.The synthesis of BINAM by stereoselectivity is rare. The synthesis of binam mainly depends on the traditional synthesis methods, although some stereoselective oxidative coupling reports have been reported.Unlike BINOL, the oxidative coupling method is not very effective.Acid catalyzed diarylhydrazine [3o 3]-rearrangement may be an effective and universal method for the synthesis of racemic or optically active BINAM derivatives.Recently, the K 眉 rti and List groups used chiral phosphoric acid to catalyze the synthesis of photoactive binaphthylamine from diarylhydrazine [3o 3]-rearrangement.Unfortunately, in practice, the synthesis of diarylhydrazine and chiral phosphoric acid is very difficult.Stereoselective, convenient and effective synthesis of diversified BINAM derivatives will have a profound impact on the discovery of new chiral biarene ligands and catalysts.This paper describes an effective and practical method for [3H3]-rearrangement of photoactive BINAM derivatives.1.Metal catalyzed cross-coupling of halogenated aromatics with amine compounds was used to synthesize menthoxy carbonyl protected diaryl hydrazine. Different ligand and metal combinations, reaction temperature, reaction time and solvent were screened.To obtain the best reaction conditions, making the highest yield.2.3.The hydrolysis conditions of amide bond of 52a and other compounds were explored. Binaphthylamine and its derivatives were obtained by acid hydrolysis and alkaline hydrolysis, respectively.The yield is very high.The ee value of the products detected by HPLC was above 99%.In this paper, the optically active binaphthylamine and its derivatives are designed and synthesized, which provides a feasible and effective way for the synthesis of chiral binaphthylamine and its derivatives, and lays a foundation for the further application of chiral binaphthylamine.
【學(xué)位授予單位】：第四軍醫(yī)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類號(hào)】：R914

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相關(guān)期刊論文 前2條

1 張占輝,默麗萍,劉慶彬,李同雙;1,1′-聯(lián)萘-2,2′-二胺的合成及在不對(duì)稱合成中的應(yīng)用[J];有機(jī)化學(xué);2003年01期

2 宋來東,楊光中;消旋聯(lián)萘胺的氧化偶合法合成[J];化學(xué)試劑;2001年03期

本文編號(hào)：1743657