构建生物碱骨架的催化不对称碳—碳键形成反应研究
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摘要
手性含氮杂环化合物广泛存在于生物碱、药物活性分子中,也是有机合成的重要中间体。发展高效合成该类分子的方法学具有重要的意义。本文设计了多种不对称催化反应,成功构建了多种生物碱骨架,用于合成吡咯类、吲哚类生物碱,取得了非常好的结果,并首次实现了吲哚类生物碱(+)-Folicanthine的不对称催化全合成。
光学活性的二氢吡咯烷是一类有着广泛用途的有机合成中间体。异腈羧酸酯与贫电子烯烃的环化反应,一步构建多个手性中心,是合成二氢吡咯烷非常有效和原子经济的方法。本文首次实现了金鸡纳碱衍生物催化异腈羧酸酯与硝基烯烃的不对称环化反应,可以快捷高效地合成手性的二氢吡咯衍生物,发现具有6-位酚羟基的金鸡纳碱衍生物能够很好地催化该反应,对于各类底物都能取得很好的结果,得到高达99%的对映选择性。利用该不对称合成策略,通过衍生,可以进一步合成多取代的手性四氢吡咯衍生物。
光学活性的四氢吡咯和氧化吲哚螺环是一类非常重要的手性分子。本文发展了一类仿生催化的不对称1，3-偶极环加成反应,利用手性磷酸催化剂能够实现酮亚胺转化为甲亚胺叶立德,继而与贫电子烯烃高选择性地发生不对称1,3-偶极环加成反应；在温和的条件下,得到构型单一,高达99%的对映选择性。利用该合成方法,可以快速构建手性多取代四氢吡咯和氧化吲哚螺环结构,为多样性导向合成生理活性化合物提供了很好的方法学。
基于碳氢活化的交叉脱氢偶联反应是形成C-C最直接有效的手段,发展高选择性的不对称氧化偶联反应具有很大的挑战。我们利用DDQ(二氯二氰苯醌)作为氧化剂,将3-苄基吲哚衍生物氧化成α,β-不饱和亚胺中间体,通过手性噁唑啉配体与铜形成的配合物活化1,3-二羰基化合物,脱氢偶联产物获得高达98%的对映选择性。而且脱氢偶联产物可以很容易转化成高光学活性多取代吲哚啉并环结构。
六氢吡咯吲哚类骨架广泛存在于生物碱以及生物活性分子中。我们通过布朗斯特酸活化3-羟基氧化吲哚和烯酰胺的反应,高收率和高立体选择性地得到了含有手性季碳的3,3’-双取代的氧化吲哚产物,对映选择性高达96%ee。以此反应为基础,首次实现了天然产物生物碱(+)-Folicanthine的催化不对称全合成。
Chiral cyclic molecules, especially those nitrogen-containing skeletons, are core structural element commonly present in numerous nature products and biologically active molecules, as well as important buiding blocks in organic synthesis. In this dissertation, we have developed several enantioselective catalytic methods as a broadly applicable to access key chiral building blocks, and have accomplished the first enantioselective total synthesis of (+)-Folicanthine.
Optically active2,3-dihydropyrroles are important unsaturated heterocyclic compounds, which can not only be transformed into multisubstituted pyrrolidines for the further synthesis of chiral building blocks, but also have been applied to the total synthesis of natural products. We have disclosed the first asymmetric catalytic cycloaddition reaction of α-substituted isocyanoesters with nitroolefins by cinchona alkaloid derivatives to yield2,3-dihydropyrroles with excellent diastereo-and enantioselectivities (up to＞20/1dr,＞99%ee). Cinchona alkaloids bearing a C6'-hydroxy, which can serve as bifunctional organocatalysts, showed much higher stereoselectivity than their parent molecules. The applications of this asymmetric cycloaddition in the synthesis of structurally diverse pyrrolidines have been demonstrated by diastereoselective reduction and Michael addition with phenylethynyl lithium.
Five-membered nitrogenous heterocycles, in particular, pyrrolidines and spirooxindoles, are key structural motifs prevalent in numerous biologically significant molecules and natural alkaloids. We have developed a highly efficient, so far unique, bio-inspired diversity-oriented synthesis of pyrrolidine derivative collection, which relies on the strategic use of phosphoric acid-catalyzed biomimetic transamination of keto esters and amines, the precursors of amino acids, to in situ generate azomethine ylides, which readily participated in the highly enantioselective1,3-dipolar cycloaddition with a structurally diverse range of dipolarophiles. As a result, highly functionalized pyrrolidines and spirooxindole derivatives were obtained with excellent enantioselectivity.
C-H activation-based cross-coupling reactions have emerged as robust alternatives to conventional transformations for the creation of new C-C bonds. These reactions may be limited by the absence of binding sites in carbohydrogen compounds that enable the formation of a stereochemically defined transition state for achieving high enantioselectivity. We have disclosed a unique highly enantioselective C-H activation-based oxidative coupling reaction of3-arylmethylindoles with dibenzyl malonate by using chiral Lewis acids as catalysts. The reaction proceeded probably via a conjugate addition of the chiral Lewis acid-bonded malonate ester to the vinylogous iminium cation generated from dehydrogenation of3-arylmethylindoles with DDQ. In addition, the protocol also represents a unique sp3C-H activation-based approach to access oxindole derivatives bearing quaternary stereogenic center with high optical purity.
Cyclotryptamine alkaloids constitute a large family of natural products that show fascinating biological activities. we have developed a highly enantioselective nucleophilic substitution reaction of3-hydroxyoxindoles with enecarbamates catalyzed by chiral phosphoric acids (up to96%ee), providing a new entry to3,3'-disubstituted oxindoles with creation of a quaternary all-carbon stereogenic center at the C3position. This method holds great potential in asymmetric total syntheses of hexahydropyrroloindole alkaloids. By using this protocol to prepare the key chiral building block, we accomplished the first catalytic enantioselective total synthesis of (+)-folicanthine, which was synthesized in12steps from3-hydroxyoxindole in3.7%overall yield.
光学活性的二氢吡咯烷是一类有着广泛用途的有机合成中间体。异腈羧酸酯与贫电子烯烃的环化反应,一步构建多个手性中心,是合成二氢吡咯烷非常有效和原子经济的方法。本文首次实现了金鸡纳碱衍生物催化异腈羧酸酯与硝基烯烃的不对称环化反应,可以快捷高效地合成手性的二氢吡咯衍生物,发现具有6-位酚羟基的金鸡纳碱衍生物能够很好地催化该反应,对于各类底物都能取得很好的结果,得到高达99%的对映选择性。利用该不对称合成策略,通过衍生,可以进一步合成多取代的手性四氢吡咯衍生物。
光学活性的四氢吡咯和氧化吲哚螺环是一类非常重要的手性分子。本文发展了一类仿生催化的不对称1，3-偶极环加成反应,利用手性磷酸催化剂能够实现酮亚胺转化为甲亚胺叶立德,继而与贫电子烯烃高选择性地发生不对称1,3-偶极环加成反应；在温和的条件下,得到构型单一,高达99%的对映选择性。利用该合成方法,可以快速构建手性多取代四氢吡咯和氧化吲哚螺环结构,为多样性导向合成生理活性化合物提供了很好的方法学。
基于碳氢活化的交叉脱氢偶联反应是形成C-C最直接有效的手段,发展高选择性的不对称氧化偶联反应具有很大的挑战。我们利用DDQ(二氯二氰苯醌)作为氧化剂,将3-苄基吲哚衍生物氧化成α,β-不饱和亚胺中间体,通过手性噁唑啉配体与铜形成的配合物活化1,3-二羰基化合物,脱氢偶联产物获得高达98%的对映选择性。而且脱氢偶联产物可以很容易转化成高光学活性多取代吲哚啉并环结构。
六氢吡咯吲哚类骨架广泛存在于生物碱以及生物活性分子中。我们通过布朗斯特酸活化3-羟基氧化吲哚和烯酰胺的反应,高收率和高立体选择性地得到了含有手性季碳的3,3’-双取代的氧化吲哚产物,对映选择性高达96%ee。以此反应为基础,首次实现了天然产物生物碱(+)-Folicanthine的催化不对称全合成。
Chiral cyclic molecules, especially those nitrogen-containing skeletons, are core structural element commonly present in numerous nature products and biologically active molecules, as well as important buiding blocks in organic synthesis. In this dissertation, we have developed several enantioselective catalytic methods as a broadly applicable to access key chiral building blocks, and have accomplished the first enantioselective total synthesis of (+)-Folicanthine.
Optically active2,3-dihydropyrroles are important unsaturated heterocyclic compounds, which can not only be transformed into multisubstituted pyrrolidines for the further synthesis of chiral building blocks, but also have been applied to the total synthesis of natural products. We have disclosed the first asymmetric catalytic cycloaddition reaction of α-substituted isocyanoesters with nitroolefins by cinchona alkaloid derivatives to yield2,3-dihydropyrroles with excellent diastereo-and enantioselectivities (up to＞20/1dr,＞99%ee). Cinchona alkaloids bearing a C6'-hydroxy, which can serve as bifunctional organocatalysts, showed much higher stereoselectivity than their parent molecules. The applications of this asymmetric cycloaddition in the synthesis of structurally diverse pyrrolidines have been demonstrated by diastereoselective reduction and Michael addition with phenylethynyl lithium.
Five-membered nitrogenous heterocycles, in particular, pyrrolidines and spirooxindoles, are key structural motifs prevalent in numerous biologically significant molecules and natural alkaloids. We have developed a highly efficient, so far unique, bio-inspired diversity-oriented synthesis of pyrrolidine derivative collection, which relies on the strategic use of phosphoric acid-catalyzed biomimetic transamination of keto esters and amines, the precursors of amino acids, to in situ generate azomethine ylides, which readily participated in the highly enantioselective1,3-dipolar cycloaddition with a structurally diverse range of dipolarophiles. As a result, highly functionalized pyrrolidines and spirooxindole derivatives were obtained with excellent enantioselectivity.
C-H activation-based cross-coupling reactions have emerged as robust alternatives to conventional transformations for the creation of new C-C bonds. These reactions may be limited by the absence of binding sites in carbohydrogen compounds that enable the formation of a stereochemically defined transition state for achieving high enantioselectivity. We have disclosed a unique highly enantioselective C-H activation-based oxidative coupling reaction of3-arylmethylindoles with dibenzyl malonate by using chiral Lewis acids as catalysts. The reaction proceeded probably via a conjugate addition of the chiral Lewis acid-bonded malonate ester to the vinylogous iminium cation generated from dehydrogenation of3-arylmethylindoles with DDQ. In addition, the protocol also represents a unique sp3C-H activation-based approach to access oxindole derivatives bearing quaternary stereogenic center with high optical purity.
Cyclotryptamine alkaloids constitute a large family of natural products that show fascinating biological activities. we have developed a highly enantioselective nucleophilic substitution reaction of3-hydroxyoxindoles with enecarbamates catalyzed by chiral phosphoric acids (up to96%ee), providing a new entry to3,3'-disubstituted oxindoles with creation of a quaternary all-carbon stereogenic center at the C3position. This method holds great potential in asymmetric total syntheses of hexahydropyrroloindole alkaloids. By using this protocol to prepare the key chiral building block, we accomplished the first catalytic enantioselective total synthesis of (+)-folicanthine, which was synthesized in12steps from3-hydroxyoxindole in3.7%overall yield.
引文
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