通过不对称有机催化的方法合成具有季碳中心的手性化合物
发布时间：2019-06-27 18:26
【摘要】：许多具有生物活性分子、药物、天然产物都具有手性季碳中心,季碳中心的构建一直是不对称催化领域研究的热点,同时也是一项极具挑战性的工作。近些年来,pyrroloindolines及furoindolines的不对称合成,以及含三氟甲基的季碳中心的构建引起了有机合成化学家们的广泛关注。本论文通过用不对称有机催化的方法实现了对其的合成,主要内容包括： 1.通过手性双环胍催化的相转移烷基化反应,高立体选择性合成具有手性季碳中心的pyrroloindolines和furoindolines 我们发展了手性双环胍盐与碘化锌联合催化体系,在相转移条件下以3位单取代的吲哚酮及活化的溴代烷烃为底物,高立体选择性合成具有生物活性及手性季碳中心的pyrroloindolines及furoindolines。该研究在以下几方面取得重要突破：1)首次用不对称有机催化的方法高立体选择性集中合成了pyrroloindolines及furoindolines；2)首次报道了手性双环胍盐与碘化锌联合催化体系；3)首次证明了手性双环胍盐在弱的无机碱条件下可以作为相转移催化剂使用,极大地丰富了手性双环胍盐在不对称有机催化领域的应用；4)通过改变催化剂的手性源可以高产率高立体选择性得到目标产物的两个对映异构体。 2.硫醇与酰胺活化的β-三氟甲基双取代烯烃的不对称共轭加成反应 首次合成了酰胺活化的p-三氟甲基双取代烯烃,并且发现生物碱衍生的手性催化剂与合适的无机碱联用可以在不影响对映选择性的前提下极大地提高反应的活性。首次用酰胺活化的β-三氟甲基双取代的烯烃与硫醇的不对称共轭加成反应,合成了手性中心含有三氟甲基的叔硫醚及叔硫醇。反应得到产物酰胺经过简单地结构修饰可以转化成相应的酯、酸、酮、磺酰胺,有利于合成多种具有生物活性的化合物。
[Abstract]:Many bioactive molecules, drugs and natural products all have chiral quaternary carbon centers. The construction of quaterpillar carbon centers has always been a hot topic in the field of asymmetric catalysis, and it is also a very challenging work. In recent years, the asymmetric synthesis of pyrroloindolines and furoindolines and the construction of quaternary carbon centers containing trifluoromethyl have attracted the attention of organic synthetic chemists. In this paper, the synthesis of asymmetric organic catalysis was realized by using asymmetric organic catalysis, the main contents of which are as follows: 1. By phase transfer alkylation catalyzed by chiral dicycloguanidine, pyrroloindolines and furoindolines with chiral quaternary carbon center were synthesized by high stereoselectivity. We developed a combined catalytic system of chiral dicycloguanidine salt and zinc iodide. Under the condition of phase transfer, pyrroloindolines and furoindolines. with biological activity and chiral quaternary carbon center were synthesized with 3-position monosubstituted indolone and activated brominated alkane as substrate. This study has made important breakthroughs in the following aspects: 1) pyrroloindolines and furoindolines;2 were synthesized by asymmetric organic catalysis for the first time. The combined catalytic system of chiral dicycloguanidine salt and zinc iodide was reported for the first time. 3) it was proved for the first time that chiral dicycloguanidine salt can be used as phase transfer catalyst under weak inorganic base conditions, which greatly enriches the application of chiral dicycloguanidine salt in asymmetric organic catalysis. 4) two enantiomers of the target product can be obtained by changing the chiral source of the catalyst with high yield and high stereoselectivity. two銆，
本文编号：2507033
[Abstract]:Many bioactive molecules, drugs and natural products all have chiral quaternary carbon centers. The construction of quaterpillar carbon centers has always been a hot topic in the field of asymmetric catalysis, and it is also a very challenging work. In recent years, the asymmetric synthesis of pyrroloindolines and furoindolines and the construction of quaternary carbon centers containing trifluoromethyl have attracted the attention of organic synthetic chemists. In this paper, the synthesis of asymmetric organic catalysis was realized by using asymmetric organic catalysis, the main contents of which are as follows: 1. By phase transfer alkylation catalyzed by chiral dicycloguanidine, pyrroloindolines and furoindolines with chiral quaternary carbon center were synthesized by high stereoselectivity. We developed a combined catalytic system of chiral dicycloguanidine salt and zinc iodide. Under the condition of phase transfer, pyrroloindolines and furoindolines. with biological activity and chiral quaternary carbon center were synthesized with 3-position monosubstituted indolone and activated brominated alkane as substrate. This study has made important breakthroughs in the following aspects: 1) pyrroloindolines and furoindolines;2 were synthesized by asymmetric organic catalysis for the first time. The combined catalytic system of chiral dicycloguanidine salt and zinc iodide was reported for the first time. 3) it was proved for the first time that chiral dicycloguanidine salt can be used as phase transfer catalyst under weak inorganic base conditions, which greatly enriches the application of chiral dicycloguanidine salt in asymmetric organic catalysis. 4) two enantiomers of the target product can be obtained by changing the chiral source of the catalyst with high yield and high stereoselectivity. two銆，
本文编号：2507033
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