本文關(guān)鍵詞： oxy-Nazarov 5-羥基環(huán)戊烯酮 1 3-二氧雜環(huán)戊-2-酮 苯并1 4二氧雜環(huán)己-2-酮　出處：《重慶大學(xué)》2014年碩士論文　論文類型：學(xué)位論文

【摘要】：經(jīng)典Nazarov環(huán)化反應(yīng)是構(gòu)建多官能團(tuán)取代的五元碳環(huán)的周環(huán)反應(yīng)，但因其區(qū)域選擇性與立體選擇性的控制等問題，使得該反應(yīng)在有機(jī)合成中的應(yīng)用具有一定的局限性。 我們課題組發(fā)展了具有廣泛底物適用性的多種類型的還原oxy-Nazarov電環(huán)化新方法，具有以下特點(diǎn)：（1）立體專一性的構(gòu)筑多取代、多官能團(tuán)化的羥基環(huán)戊烯酮；（2）通過在環(huán)化底物中引入C2對(duì)稱的手性二醇為輔基，可有效實(shí)現(xiàn)不對(duì)稱的還原oxy-Nazarov環(huán)化反應(yīng)（Scheme1）。 本論文第一部分針對(duì)1984年Ramage等報(bào)道（J. Chem. Soc., Perkin Trans. I1984,1531-1537）的1,3-二氧雜環(huán)戊-2-酮（1,3-dioxolan-2-one）衍生物在二異丁基氫化鋁還原條件下反應(yīng)研究的實(shí)驗(yàn)結(jié)果進(jìn)行了重復(fù)與驗(yàn)證。我們將肉桂醛的Wittig反應(yīng)生成的構(gòu)型異構(gòu)體（2-24E）和（2-24Z）經(jīng)柱色譜分離純化后，分別在二異丁基氫化鋁還原條件下反應(yīng)，，發(fā)現(xiàn)只有EE構(gòu)型異構(gòu)體發(fā)生立體專一性的還原環(huán)化反應(yīng)，生成反式構(gòu)型的4-苯基-5-羥基-環(huán)戊烯酮產(chǎn)物（2-25），從而確證了早期文獻(xiàn)報(bào)道中推測(cè)的環(huán)化產(chǎn)物是oxy-Nazarov電環(huán)化反應(yīng)的結(jié)果（Scheme2）。 本文第二部分描述了研究了一種新型的由鄰苯二酚衍生的1,4-二氧雜環(huán)己-2-酮（benzo[b]-1,4-dioxin-2-one）環(huán)化前體（2-31）的設(shè)計(jì)、合成及在二異丁基氫化鋁還原條件下立體專一性的生成環(huán)化產(chǎn)物（2-34）的oxy-Nazarov電環(huán)化反應(yīng)研究（Scheme3）。
[Abstract]:The classical Nazarov cyclization reaction is a ring reaction of constructing a five-member carbon ring replaced by multifunctional groups. However, due to the control of its regioselectivity and stereoselectivity, the application of the reaction in organic synthesis is limited to a certain extent. Our group has developed a variety of new reduction oxy-Nazarov electrocyclization methods with extensive substrate applicability, with the following characteristics: 1) the construction of stereospecific substitution. The asymmetric reduction of oxy-Nazarov cyclization reaction can be realized effectively by introducing C2 symmetric chiral diol into the cyclized substrate. In the first part of this thesis, we repeat and verify the experimental results of the reaction of Ramage et al., J. Chem. Soc., Perkin Trans. I1984, 1531-1537) in the reduction condition of diisobutyl aluminum hydride. The configuration isomers of cinnamaldehyde produced by Wittig reaction were separated and purified by column chromatography. Under the reduction conditions of diisobutyl aluminum hydride, only EE isomers were found to have stereospecific reductive cyclization. A trans-configuration of 4-phenyl-5-hydroxy-cyclopentenone was obtained. It was confirmed that the cyclization product in the early literature was the result of oxy-Nazarov electrocyclization. In the second part of this paper, we describe the design of a new cyclization precursor, benzo [b] -1n 4-dioxin-2-one, derived from catechol. Oxy-Nazarov electrocyclization of cyclization product of stereospecific synthesis and reduction of diisobutyl aluminum hydride under the condition of stereospecific cyclization.
【學(xué)位授予單位】：重慶大學(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1條

1 錢建華，劉琳;Wittig反應(yīng)及Wittig—Horner反應(yīng)在有機(jī)合成上的應(yīng)用[J];石油化工高等學(xué)校學(xué)報(bào);1994年04期

本文編號(hào)：1534425