有机催化的不对称Aldol反应及其它相关反应研究
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摘要
不对称有机合成是当代有机合成的最具有吸引力的领域之一。作为不对称合成的一个新方法，对映选择性的有机催化已经成为越来越普遍应用的方法。在本论文中，多官能化的手性有机催化剂的设计和合成是十分重要的。因此，我们发展了一系列双功能、性能可调的手性二级胺-双酰胺衍生物作为有机催化剂。在催化剂分子中，存在两个不同的用于反应的作用位点。这样，通过改变不同的基团，可以有效地精微调控催化剂在不对称反应中的活性和选择性。催化剂的基本结构单元如下：
为了检验新型有机催化剂的催化活性，我们研究了硫代四氢吡喃酮和各种醛的直接不对称Aldol反应。我们发现对于这一类反应，上述催化剂表现出显著的催化活性。各种醛与硫代四氢吡喃酮反应，高产率高立体选择性地得到反应产物，反应产率最高达到91％，ee值最高达到99％，dr值最高达到99∶1。
水是一种环境友好、安全、价廉的溶剂。人们对使用水作为添加物或者取代传统的有机溶剂的有机反应已经进行了大量的研究。相反，尽管在盐水溶液中的反应效果可以比在水中的效果要好，但是较少有使用盐水溶液作为反应介质的报道。我们研究了在盐水溶液中使用双功能可调的有机催化剂催化的环己酮和醛的不对称Aldol反应。使用这类二级胺-双酰胺有机催化剂在盐水溶液中的反应，得到了高对映选择性和非对映选择性。
α-取代的磷酸酯化合物是一类重要的生物活性分子，这类化合物被广泛用作酶抗体、抗菌素、抗HIV药物以及催化抗体的半抗原等。因此，α-取代的磷酸酯化合物和它的官能化衍生物的合成是一个十分重要的课题。我们初步实验了对映选择性的有机催化二烷基亚磷酸酯和醛的反应不对称合成α-羟基膦酸酯。
从简单的原料各种取代苯酚出发，通过Grubbs催化剂催化的烯烃交叉复分解反应合成了一系列含氧原子的α，β-不饱和醛化合物。
Asymmetric organic synthesis is one of the most attractive research areas in organic synthesis. As a new method for asymmetric synthesis, enantioselective organocatalysis has become more and more popular. In this context, the design and synthesis of multifunctional chiral organocatalysts are of great importance. Accordingly, we have prepared a series of bifunctional chiral secondary amine-amides in which one catalyst molecule possesses two reaction-promoting functionalities. Thus, the activity and selectivity can be tuned by a simple modification in the structural motif of the catalyst. The basic structure units of the catalysts are outlined as below.
In order to examine the catalytic activity of the new catalysts, we have carried out the direct asymmetric Aldol reaction of tetrahydro-4H-thiopyran-4-one with aldehydes. It has been found that the above catalysts have remarkable activities for this particular reaction. The reactions of aromatic aldehydes with tetrahydro-4H-thiopyran-4-one afford the Aldol adducts in good to excellent yield, with enantioselectivities ranging from 97% to 99% ee.
There have been considerable efforts to develop organic reactions using water as an additive or a solvent instead of conventional organic solvents with respect to environmental concerns, safety, and cost. In contrast, there have been relatively few investigations using brine as the reaction media, although the reaction efficiency in brine may be superior to that in water. We examine the asymmetric Aldol reaction with cyclohexanone and aldehyde using tunable and bifunctional organocatalysts in aqueous media. To our delight, we obtain high diastereo- and enantioselectivities in brine with these chiral diamide organocatalysts.
α-Substituted phosphonates are particularly important in connection with their remarkable biological activities. They have been found widespread use as enzyme inhibitors, antibacterial agents, anti-HIV agents, botryticides, and haptens for catalytic antibodies. For these reasons, the synthesis ofα-substituted phosphonates and their functionalized derivatives is an important objective. We have initially examined organocatalytic enantioselective synthesis ofα-Hydroxy phosphonates through the reaction of dialkyl phosphates and aldehydes.
A series ofα,β-unsaturated aldehydes have been prepared in high yields through Ru-catalyzed cross metathesis reactions of various substituted allyloxy-benzene with (E)-but-2-enal.
为了检验新型有机催化剂的催化活性，我们研究了硫代四氢吡喃酮和各种醛的直接不对称Aldol反应。我们发现对于这一类反应，上述催化剂表现出显著的催化活性。各种醛与硫代四氢吡喃酮反应，高产率高立体选择性地得到反应产物，反应产率最高达到91％，ee值最高达到99％，dr值最高达到99∶1。
水是一种环境友好、安全、价廉的溶剂。人们对使用水作为添加物或者取代传统的有机溶剂的有机反应已经进行了大量的研究。相反，尽管在盐水溶液中的反应效果可以比在水中的效果要好，但是较少有使用盐水溶液作为反应介质的报道。我们研究了在盐水溶液中使用双功能可调的有机催化剂催化的环己酮和醛的不对称Aldol反应。使用这类二级胺-双酰胺有机催化剂在盐水溶液中的反应，得到了高对映选择性和非对映选择性。
α-取代的磷酸酯化合物是一类重要的生物活性分子，这类化合物被广泛用作酶抗体、抗菌素、抗HIV药物以及催化抗体的半抗原等。因此，α-取代的磷酸酯化合物和它的官能化衍生物的合成是一个十分重要的课题。我们初步实验了对映选择性的有机催化二烷基亚磷酸酯和醛的反应不对称合成α-羟基膦酸酯。
从简单的原料各种取代苯酚出发，通过Grubbs催化剂催化的烯烃交叉复分解反应合成了一系列含氧原子的α，β-不饱和醛化合物。
Asymmetric organic synthesis is one of the most attractive research areas in organic synthesis. As a new method for asymmetric synthesis, enantioselective organocatalysis has become more and more popular. In this context, the design and synthesis of multifunctional chiral organocatalysts are of great importance. Accordingly, we have prepared a series of bifunctional chiral secondary amine-amides in which one catalyst molecule possesses two reaction-promoting functionalities. Thus, the activity and selectivity can be tuned by a simple modification in the structural motif of the catalyst. The basic structure units of the catalysts are outlined as below.
In order to examine the catalytic activity of the new catalysts, we have carried out the direct asymmetric Aldol reaction of tetrahydro-4H-thiopyran-4-one with aldehydes. It has been found that the above catalysts have remarkable activities for this particular reaction. The reactions of aromatic aldehydes with tetrahydro-4H-thiopyran-4-one afford the Aldol adducts in good to excellent yield, with enantioselectivities ranging from 97% to 99% ee.
There have been considerable efforts to develop organic reactions using water as an additive or a solvent instead of conventional organic solvents with respect to environmental concerns, safety, and cost. In contrast, there have been relatively few investigations using brine as the reaction media, although the reaction efficiency in brine may be superior to that in water. We examine the asymmetric Aldol reaction with cyclohexanone and aldehyde using tunable and bifunctional organocatalysts in aqueous media. To our delight, we obtain high diastereo- and enantioselectivities in brine with these chiral diamide organocatalysts.
α-Substituted phosphonates are particularly important in connection with their remarkable biological activities. They have been found widespread use as enzyme inhibitors, antibacterial agents, anti-HIV agents, botryticides, and haptens for catalytic antibodies. For these reasons, the synthesis ofα-substituted phosphonates and their functionalized derivatives is an important objective. We have initially examined organocatalytic enantioselective synthesis ofα-Hydroxy phosphonates through the reaction of dialkyl phosphates and aldehydes.
A series ofα,β-unsaturated aldehydes have been prepared in high yields through Ru-catalyzed cross metathesis reactions of various substituted allyloxy-benzene with (E)-but-2-enal.
引文
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