【作者】 王春燕；

【导师】 潘远江；

【作者基本信息】 浙江大学 ， 有机化学， 2007， 博士

【摘要】 氯化铟是一种无毒、对水和空气都不敏感的路易斯酸，近年来的研究表明，它能促进多种类型的有机反应。随着人们对环境问题的日益关注，有关氯化铟在有机反应中的应用研究已经越来越引起广大化学工作者的兴趣。本文研究了氯化铟在炔烃及羰基化合物还原反应中的应用：通过氯化铟参与的炔基膦（硅）类化合物的铟氢化反应合成了一系列的烯基膦（硅）类化合物；而通过InCl₃／Al体系下各种羰基化合物还原反应合成了一系列的1，2—邻二醇和蒽类化合物。本论文主要包括四个部分：第一部分以炔基膦酸酯类化合物为底物，研究了其在InCl₃-NaBH₄-MeCN体系中的还原反应。首先，以苯基炔基磷酸乙酯为底物，通过调控反应条件以高转化率选择性地得到了（E）—苯基烯基磷酸乙酯，在确定了反应条件后，考察了不同取代基对反应结果的影响。研究表明，当底物中含有共轭结构时反应的选择性和产率要比脂肪族底物高得多，而对于芳香族底物，苯环上连有吸电子基团时，反应的选择性和产率要比连有供电子基团时稍好。最后，对反应的机理进行了讨论，并且通过氘代实验进行了验证。通过本部分的研究，我们探索出了一条氯化铟参与的合成（E）—芳基烯基膦酸酯类化合物的有效途径。第二部分以炔基硅类化合物为底物，研究了其在InCl₃-NaBH₄-THF体系中的还原反应。首先，以苯基炔基三甲基硅烷为底物，通过优化反应条件高转化率选择性地得到了（E）—苯基烯基三甲基硅烷。在确定了反应条件后，考察了不同取代基对反应结果的影响，发现取代基电子效应对该反应的影响和炔基膦酸酯类化合物的还原反应是类似的。同时我们对氯化铟参与的炔基膦酸酯类化合物和炔基硅类化合物的还原反应进行了比较，发现除了反应溶剂不同外，在炔基硅类化合物的还原反应中产生了过度还原产物，而这一现象在相应的炔基膦酸酯类化合物的反应中是不存在的，最后，根据反应机理推测了其中可能的原因。通过本部分的研究，我们探索出了一条氯化铟参与的合成（E）—芳基烯基硅类化合物的有效途径。第三部分较为系统地研究了InCl₃／Al体系中二苯甲酮类化合物、苯甲醛类化合物及苯乙酮类化合物的片呐醇偶联反应。首先，以二苯甲酮为底物，优化了其在InCl₃／Al体系中发生片呐醇反应的条件，在优化条件的过程中研究了其直接还原的产物与片呐醇产物之间的比例随反应温度的变化规律，发现高温容易使底物发生片呐醇偶联反应，而低温则使反应倾向于生成直接还原的产物。在优化的条件下，分别研究了不同取代的二苯甲酮类化合物、苯甲醛类化合物、苯乙酮类化合物的片呐醇偶联反应，研究表明，它们的片呐醇反应的活性是依次降低的，且苯环上连有吸电子基团时，反应的活性要比连有供电子基时好，但当邻位上有取代基时，由于空间位阻的原因底物倾向于被直接还原。最后，以1，5—二羰基化合物为底物研究了其在InCl₃／Al体系中的分子内片呐醇偶联反应。通过本部分的研究，我们合成了一系列不同取代的邻二醇类化合物，提供了一条氯化铟参与的合成邻二醇类化合物的有效途径。第四部分较为系统地研究了在InCl₃／Al体系中蒽酮（醌）类化合物的还原反应。研究表明蒽酮（醌）类化合物在InCl₃／Al体系中生成的不是片呐醇产物和直接还原的产物而是蒽和二氢蒽类化合物。通过调控反应条件将蒽酮类化合物的还原产物完全控制为蒽类化合物。同时，研究了不同取代的蒽醌类化合物在InCl₃／Al体系中的反应。通过本部分的研究，我们提供了一条氯化铟参与的方便的合成蒽类化合物的有效途径。此外，本文还简要综述了近年来氯化铟促进的有机反应。更多还原

【Abstract】 As a Lewis acid, Indium chloride is of excellent qualities such as nontoxicityand compatibility with water and air. It can promote many kinds of organic reactions.Recently, application of Indium chloride in organic reactions has attracted more andmore chemists’ interest. In this thesis, application of Indium chloride in the reductionof alkynes and carbonyl compounds was studied. This thesis consists of foursections.In section 1, reduction of alkynylphosphates in InCl₃-NaBH₄-MeCN systemwas investigated, in which a series of （E）-arylvinylphosphates were obtained in highyield and selectivity. First, the conditions of the reaction were optimized withphenylalkynylphosphate as the substrate. Under the optimized conditions the effectof the different substitutents on the reaction were investigated. It was found thatbetter yield and selectivity were obtained when there was conjugate structure in thesubstrate. For aromatic substrates, when the hydrogen atom of benzene ring wassubstituted by an electron-donating group, the yield and stereoselcetivity decreasedslightly, while hydrogen atom of benzene ring was substituted by anelectron-withdrawing group the yield and selectivity were rather high. Finally,possible mechanism was proposed. Based on the reaserch of this part, we developeda convenient and effective way to synthesize （E）-arylvinylphosphates.In section 2, reduction of alkynylsilanes in InCl₃-NaBH₄-THF system wasinvestigated, in which a series of （E）-arylvinylsilanes were obtained in high yieldand selectivity. First, the conditions of the reaction were optimized withphenylalkynylsilane as the substrate. Under the optimized conditions the effect of thedifferent substitutents on the reaction were investigated. It was found that electronic effect was similar with the reduction of alkynylphosphates. On the other hand, therewere two defferences between reductions of alkynylphosphates and alkynylsilanes:（1） solvent; （2） In reductions of alkynylsilanes in InCl₃-NaBH₄-THF systemover-reduced products were detected, however, they were not dectected in reductionsof alkynylphosphates. The possible reason was discussed according to themechanism. In this section, we afforded a convenient and effective way to synthesize（E）-arylvinylsilanes.In section 3, pinacol coupling reactions of aldehydes and ketones in aqueousmedia with InCl₃/Al reagent were studied systemically, in which 1, 2-diols wereobtained in moderate to good yield. First, the conditions of the reaction wereoptimized with benzophenone as the substrate. It was found that higher temperaturewas in faver of the pinacol coupling of benzophenone in this system. Under theoptimized conditions the pinacol coupling reactions of the benzophenones,benzaldehydes and acetophenones with different substitutents were investigatedsystemically, which showed that their reaction activity was weakened in sequence.The substrates bearing electron-withdrawing groups had higher activity than thosebearing electron-donating groups. Because of steric hindrance the correspondingreduction products were obtained as main products when the substrates bear thesubstituents ortho to ketones. Furthermore, InCl₃/Al mediated intramolecule pinacolreactions of 1, 5-dicarbonyl compounds were investigated. In this section, weafforded a convenient and effective way to synthesize 1, 2-diols.In section 4, InCl₃/Al mediated reductions of anthrones （9, 10-anthraquinones）were investigated. Under the optimized conditions in section 3, anthrones werereduced to anthrances and 9, 10-dihydroanthrances instead of the pinacol products orthe corresponding alcohols. The reduced products of anthrones could be controlledto anthrances by optimizing the reaction conditions. Furthermore, InCl₃/Al mediated reductions of anthrones bearing different substitutents were investigated. On theother hand, InCl₃/Al mediated reductions of 9, 10-anthraquinones were studied. Inthis section, we afforded a convenient and effective way to synthesize anthrancesfrom anthrones.In addition, InCl₃-promoted organic reactions were generally reviewed.更多还原