三苯基膦促进有机物脱氧生成不饱和键反应的研究
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摘要
近年来,有机膦催化的有机合成反应发展迅速,三苯基膦及其衍生物则是有机膦中最重要的一类,它是有机合成中常用的反应试剂和金属络合催化剂的配体之一。三苯基膦在反应当中不仅仅只充当配体作用,在有些合成反应中它还可以充当促进剂——脱氧剂的作用。与过渡金属催化剂相比,三苯基膦具有无毒无害、价廉易得、反应体系无重金属残留、易于修饰与负载、易于从产物中分离出来重复利用等特点,符合当前大力提倡的绿色化学的要求。
本课题以三苯基膦促进的脱氧化为主要线索,通过不断尝试三苯基膦在不同反应体系中所起的作用。在本论文所描述的两个反应中,三苯基膦被证明能够促进有机物脱去氧原子并形成新的碳-碳键或生成新的不饱和键：
1)对甲氧基三苯基膦促进的芳醛与丁烯二酸酐脱氧生成(E)-芳亚甲基丁二酸甲酯的研究。(E)-芳亚甲基丁二酸酯是一种重要的合成单体,可以被用来合成1,4-二苯基丁二烯衍生物、2,3-丁烯二醇、(Z)-α-乙酰基丙烯酸酯,(Z)-β-芳基亚甲基丁二酸酯衍生物,然而其的合成手段至今都不能让人满意。本论文研究出了一种温和有效的合成(E)-芳亚甲基丁二酸酯的方法,该方法利用对甲氧基三苯基膦促进的马来酸衍生物与芳香醛之间两组份反应来实现,通过对底物,添加剂,溶剂的筛选以及温度和时间的控制,我们可以简便的高选择性的制备(E)-2-芳亚甲基丁二酸甲酯,产率中等到优秀。据我们所知,我们开发了一种直接合成重要有机合成中间体(E)-2-芳亚甲基丁二酸甲酯的新方法。
2)三苯基膦促进的2,4-戊二炔-1-醇脱氧生成取代的联烯炔反应研究。联烯炔是一种合成复杂化合物或者工业产品的重要前驱体,同时它还是重要的有机合成中间体,此外,还有许多联烯炔化合物表现出了良好的生物活性。在继承本实验室工作的基础上,我们成功开发出一种以共轭二炔醇化合物合成联烯炔的方法。该方法以2,4-戊二炔-1-醇为底物,在三苯基膦促进下一步脱氧生成三取代联烯炔衍生物。同时这也是第一例直接由炔丙醇直接生成丙二烯键的方法,反应开启了简易合成具有联烯炔结构天然产物的新思路。
Tremendous advancement has been made in organic phosphorus catalyzed or mediated reactions in organic synthetic reaction. It is shown that triphenylphosphine and its derivates play an important role in organic synthesis.They are primarily used as intermediates of organic phosphorus flame retardants and phosphorus ligands in biphasic water soluble catalysts. Not only regarded as ligands of transitional-metal, triphenylphosphine can also serve as promoter--deoxygenation agent in some case. Compared with transitional-metal catalyst, triphenylphosphine has the following feature:non-toxic;inexpensive and readily available; no heavy metals residue;easy to modify and load; separate conveniently for reuse and so on. All this make triphenylphosphine-promoted reaction meet with essential requirements of green chemistry.
This dissertation take PPh3 promoted deoxygention as a key clue and aims to search for role that PPh3 played in divers reaction systems. It was proven that PPh3 can work as an intermediate to promote organic compounds containing oxgen atom deoxygenation for the formation of new carbon-carbon bond or unsaturated bond:
1)Research on the synthesis of (E)-2-benzylidenesuccinates via tris(4-anisyl)phosphine-controlled reaction of arylaldehydes with maleic anhydride or dimethyl maleate. Arylmethylidenesuccinates, one of the important synthons, have been employed to synthesize 1,4-diphenylbutadiene derivatives,2,3-butanediol, (Z)-methyl a-(acetoxy)acrylates and (E)-β-aryl itaconate derivatives. However, a considerable body of synthetic methods for arylmethylidenesuccinates has not been entirely satisfactory. In our thesis, we have described the reaction of benzaldehydes with maleic anhydride or dimethyl maleate controlled by P(p-MeOC6H4)3. Through altering reaction substrates, additive, solvent and temperature we can get (E)-2-benzylidenesuccinates with high stereoselectivity in moderate to good yields under mild conditions.To the best of our knowledge, this protocol opened up a direct way for the synthesis of (E)-2-benzylidensuccinates, which are very important potential organic intermediates in organic synthesis.
2) Study on a facile synthesis of trisubstituted allenynes via phosphine-mediated deoxygenation of 2,4-pentadiyne-l-ol.Allenynes as a suite of highly unsaturated compounds can serve as precursors in the synthesis of highly complex or industrial importance and they are also important intermediates in organic synthesis.In addition, allenynes are present in many natural products and compounds with interesting biological activities Based on the study of our laboratory, a facile method for the synthesis of trisubstituented allenynes has been developed, involving the PPh3-mediated deoxygenation of propargyl alcohols.To the best of our knowledge, this is the first example of the preparation of an allenyne derivative directly from propargyl alcohol using an organocatalyst. This protocol casts light on future easy synthesis of natural product with the structure of conjugated allene and acetylenic bond.
本课题以三苯基膦促进的脱氧化为主要线索,通过不断尝试三苯基膦在不同反应体系中所起的作用。在本论文所描述的两个反应中,三苯基膦被证明能够促进有机物脱去氧原子并形成新的碳-碳键或生成新的不饱和键：
1)对甲氧基三苯基膦促进的芳醛与丁烯二酸酐脱氧生成(E)-芳亚甲基丁二酸甲酯的研究。(E)-芳亚甲基丁二酸酯是一种重要的合成单体,可以被用来合成1,4-二苯基丁二烯衍生物、2,3-丁烯二醇、(Z)-α-乙酰基丙烯酸酯,(Z)-β-芳基亚甲基丁二酸酯衍生物,然而其的合成手段至今都不能让人满意。本论文研究出了一种温和有效的合成(E)-芳亚甲基丁二酸酯的方法,该方法利用对甲氧基三苯基膦促进的马来酸衍生物与芳香醛之间两组份反应来实现,通过对底物,添加剂,溶剂的筛选以及温度和时间的控制,我们可以简便的高选择性的制备(E)-2-芳亚甲基丁二酸甲酯,产率中等到优秀。据我们所知,我们开发了一种直接合成重要有机合成中间体(E)-2-芳亚甲基丁二酸甲酯的新方法。
2)三苯基膦促进的2,4-戊二炔-1-醇脱氧生成取代的联烯炔反应研究。联烯炔是一种合成复杂化合物或者工业产品的重要前驱体,同时它还是重要的有机合成中间体,此外,还有许多联烯炔化合物表现出了良好的生物活性。在继承本实验室工作的基础上,我们成功开发出一种以共轭二炔醇化合物合成联烯炔的方法。该方法以2,4-戊二炔-1-醇为底物,在三苯基膦促进下一步脱氧生成三取代联烯炔衍生物。同时这也是第一例直接由炔丙醇直接生成丙二烯键的方法,反应开启了简易合成具有联烯炔结构天然产物的新思路。
Tremendous advancement has been made in organic phosphorus catalyzed or mediated reactions in organic synthetic reaction. It is shown that triphenylphosphine and its derivates play an important role in organic synthesis.They are primarily used as intermediates of organic phosphorus flame retardants and phosphorus ligands in biphasic water soluble catalysts. Not only regarded as ligands of transitional-metal, triphenylphosphine can also serve as promoter--deoxygenation agent in some case. Compared with transitional-metal catalyst, triphenylphosphine has the following feature:non-toxic;inexpensive and readily available; no heavy metals residue;easy to modify and load; separate conveniently for reuse and so on. All this make triphenylphosphine-promoted reaction meet with essential requirements of green chemistry.
This dissertation take PPh3 promoted deoxygention as a key clue and aims to search for role that PPh3 played in divers reaction systems. It was proven that PPh3 can work as an intermediate to promote organic compounds containing oxgen atom deoxygenation for the formation of new carbon-carbon bond or unsaturated bond:
1)Research on the synthesis of (E)-2-benzylidenesuccinates via tris(4-anisyl)phosphine-controlled reaction of arylaldehydes with maleic anhydride or dimethyl maleate. Arylmethylidenesuccinates, one of the important synthons, have been employed to synthesize 1,4-diphenylbutadiene derivatives,2,3-butanediol, (Z)-methyl a-(acetoxy)acrylates and (E)-β-aryl itaconate derivatives. However, a considerable body of synthetic methods for arylmethylidenesuccinates has not been entirely satisfactory. In our thesis, we have described the reaction of benzaldehydes with maleic anhydride or dimethyl maleate controlled by P(p-MeOC6H4)3. Through altering reaction substrates, additive, solvent and temperature we can get (E)-2-benzylidenesuccinates with high stereoselectivity in moderate to good yields under mild conditions.To the best of our knowledge, this protocol opened up a direct way for the synthesis of (E)-2-benzylidensuccinates, which are very important potential organic intermediates in organic synthesis.
2) Study on a facile synthesis of trisubstituted allenynes via phosphine-mediated deoxygenation of 2,4-pentadiyne-l-ol.Allenynes as a suite of highly unsaturated compounds can serve as precursors in the synthesis of highly complex or industrial importance and they are also important intermediates in organic synthesis.In addition, allenynes are present in many natural products and compounds with interesting biological activities Based on the study of our laboratory, a facile method for the synthesis of trisubstituented allenynes has been developed, involving the PPh3-mediated deoxygenation of propargyl alcohols.To the best of our knowledge, this is the first example of the preparation of an allenyne derivative directly from propargyl alcohol using an organocatalyst. This protocol casts light on future easy synthesis of natural product with the structure of conjugated allene and acetylenic bond.
引文
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