【摘要】：手性α-羥基-β-二羰基化合物廣泛存在于天然產(chǎn)物、藥物、農(nóng)用化學(xué)品、功能化學(xué)品中,是一類重要功能化合物的結(jié)構(gòu)單元。制備該類化合物的不對(duì)稱催化方法主要通過金屬有機(jī)不對(duì)稱催化和有機(jī)小分子不對(duì)稱催化。金屬有機(jī)不對(duì)稱催化對(duì)β-二羰基化合物的α-羥基化反應(yīng)研究的較成熟且系統(tǒng),然而不對(duì)稱有機(jī)催化的研究報(bào)道較少,需要發(fā)現(xiàn)高效、安全、廉價(jià)的催化體系。 手性β-氨基醇類化合物作為催化劑廣泛應(yīng)用于催化Aldole反應(yīng)、Michael加成反應(yīng)、烯烴環(huán)氧化等反應(yīng)。在本課題組研究苯氧氨基醇催化劑的基礎(chǔ)上,本文研究了萘氧氨基醇作為有機(jī)催化劑催化β-酮酸酯的不對(duì)稱羥基化反應(yīng)。以商業(yè)易得的2,7-二萘酚為原料合成了8個(gè)萘氧氨基醇催化劑(A1-A8),其中A2-A7均為未見文獻(xiàn)報(bào)道的新化合物,并使用紅外、核磁、質(zhì)譜對(duì)上述8個(gè)化合物進(jìn)行了結(jié)構(gòu)表征。其中對(duì)A8-c進(jìn)行了XRD單晶衍射分析,對(duì)其空間結(jié)構(gòu)進(jìn)行了確認(rèn)。 對(duì)A1～A8萘氧氨基醇催化劑催化β-酮酸酯不對(duì)稱羥基化的篩選,發(fā)現(xiàn)催化劑A5催化5-氯-茚酮羧酸甲酯(1a)具有較高對(duì)映選擇性,是最優(yōu)催化劑。通過對(duì)反應(yīng)溶劑、溫度、反應(yīng)時(shí)間、底物濃度等反應(yīng)條件的優(yōu)化,催化劑A5催化5-氯-茚酮羧酸甲酯羥基化獲得了63%ee及99%的產(chǎn)率。同時(shí)對(duì)催化其它14個(gè)β-酮酸酯底物進(jìn)行了研究,考察了催化劑的底物適用性。最后對(duì)A5催化1a不對(duì)稱羥基化的機(jī)理進(jìn)行了推測(cè)。
[Abstract]:Chiral 偽 -hydroxy- 尾 -dicarbonyl compounds are widely found in natural products, drugs, agricultural chemicals and functional chemicals, which are the structural units of a class of important functional compounds. The asymmetric catalytic methods for the preparation of these compounds are mainly metal-organic asymmetric catalysis and organic small molecule asymmetric catalysis. The studies on 偽 -hydroxylation of 尾 -dicarbonyl compounds by metallometallic asymmetric catalysis are more mature and systematic. However, there are few reports on asymmetric organic catalysis, which requires the discovery of efficient, safe and inexpensive catalytic systems. Chiral 尾 -aminoalcohols are widely used as catalysts for Aldole reaction and epoxidation of olefins. Based on the study of phenoxyamino alcohol catalyst, the asymmetric hydroxylation of 尾 -ketoacid ester catalyzed by naphthoxy amino alcohol as organic catalyst was studied in this paper. Eight naphthyloxyamino alcohol catalysts (A1-A8) were synthesized from commercially readily available 2-dinaphthol. Among them, A2-A7 were all new compounds not reported in the literature. The structures of the eight compounds were characterized by IR, NMR and MS. The spatial structure of A8-c was confirmed by XRD single crystal diffraction analysis. The asymmetric hydroxylation of 尾 -keto ester catalyzed by A1~A8 naphthoxy amino alcohol catalyst was screened. It was found that catalyst A5 was the best catalyst for the enantioselectivity of methyl 5-chloro-indenone carboxylate (1a). By optimizing the reaction conditions such as solvent, temperature, reaction time and substrate concentration, the catalyst A5 was used to catalyze the hydroxylation of methyl 5-chloro-indenone carboxylic acid with the yield of 63% and 99%. At the same time, the other 14 substrates of 尾 -ketoacid ester were studied, and the applicability of the substrates was investigated. Finally, the mechanism of asymmetric hydroxylation of 1a catalyzed by A5 was speculated.
【學(xué)位授予單位】：大連理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類號(hào)】：R943

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本文編號(hào)：2132292