Synthesis of Optically Active Allenecarboxylic Acid Derivatives by Asymmetric Carbonylation Reactions

我研究过烯丙基和丙炔化合物的羰基化反应。在这个项目中，我研究了这些羰基化反应的不对称版本，利用一氧化碳来完成不对称碳-碳键的形成。在具有光学活性的单齿膦配体的钯络合物催化剂的存在下，烯丙基磷酸盐羰基化反应顺利进行，得到光学活性的β， γ-不饱和羧酸酯。这是烯丙基羰基化反应的不对称版本的第一个例子。具有光学活性的丙炔磷酸在构型反转的钯络合催化剂的存在下羰基化得到轴手性的烯羧酸酯而不损失光学纯度。使用带有光学活性双齿膦配体的钯络合物催化剂进行外消旋丙炔磷酸羰基化，以动力学光学分辨率得到轴手性烯羧酸酯和回收的光学活性丙炔磷酸。这是第一个使用催化量的手性化合物不对称合成烯类化合物的例子。

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.