Synthesis of Optically Active Allenecarboxylic Acid Derivatives by Asymmetric Carbonylation Reactions

我曾研究过烯丙基和丙叉基化合物的羰基化反应。在这个项目中，我研究了这些不对称的羰基化反应，以实现使用一氧化碳形成不对称的碳-碳键。烯丙基磷酸酯在具有光学活性的单齿膦配体的钯配合物催化剂的存在下，顺利地进行羰基化反应，得到光学活性的β，γ-不饱和羧酸酯。这是第一个不对称版本的烯丙基酮基化反应的例子。光学活性的丙叉磷酸酯在钯配合物催化剂的催化下发生翻转构型，在不损失光学纯度的情况下得到轴向手性烯丙基羧酸酯。在含有光学活性双齿膦配体的钯配合物催化剂的作用下，外消旋丙叉磷酸酯通过动力学光学拆分得到手性烯丙基羧酸酯以及回收的光学活性丙叉磷酸酯。这是第一个使用催化量的手性化合物不对称合成烯丙烯化合物的例子。

I have been studied carbonylation reactions of allylic and propargylic compounds. In this project, I studied asymmetric version of these carbonylation reactions to accomplish asymmetric carbon-carbon bond formation using carbon monoxide.1. Carbonylation of allylic phosphates in the presence of a palladium complex catalyst bearing an optically active monodentate phosphine ligand proceeds smoothly to give optically active β, γ-unsaturated carboxlic acid esters. This is the first example of asymmetric version of allylic carbonylation reactions.2. Optically active propargylic phosphates are carbonylated in the presence of a palladium complex catalyst with inversion of configuration to give axially chiral allenecarboxylic acid esters without loss of optical purity.3. Carbonylation of racemic propargylic phosphates using a palladium complex catalyst bearing an optically active bidentate phosphine ligand proceeds with kinetic optical resolution to give axially chiral allenecarboxylic acid esters along with recovered optically active propargylic phosphates. This is the first example of asymmetric synthesis of allene compounds using a catalytic amount of chiral compound.