Development of Iridium-Complex-Catalyzed Highly Selective Organic Synthesis

铱配合物催化高选择性有机合成研究进展

基本信息

批准号：
14550828
负责人：
TAKEUCHI Ryo
金额：
$ 2.3万
依托单位：
AOYAMA GAKUIN UNIVERSITY (2003)Yokohama City University (2002)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2003
项目状态：
已结题

项目摘要

Much less attention has been paid to iridium complex-catalyzed reaction. The aim of this research project is to develop iridium complex-catalyzed highly selective reaction. We have studied the carbonylation of allylic phosphates and cross [2+2+2] cycloaddition of two different monoynes.1. Carbonylation of Allylic Phosphates[Ir(cod)Cl]_2 with a ligand such as P(2-furyl)_3, PPh_2C_6F_5 or AsPh_3 showed high catalytic activity for the carbonylation of allylic phosphates in the presence of alcohols to give the corresponding β,γ-unsaturated esters. The carbonylation of diethyl (E)-3-phenyl-2-opropenyl phosphate in the presence of EtOH under an initial carbon monoxide pressure of 40 kg/cm^2 at 100℃ gave ethyl (E)-4-phenyl-3-butenoate in 90% yield. No (Z)-isomer was obtained. The carbonylation of 2-alkenyl diethyl phosphates in the presence of EtOH gave a mixture of ethyl (E)-and (Z)-3-alkenoate. The stereochemistry of the starting material was lost by syn-anti isomerization of the π-allyl iridium intermediate prior to the insertion of carbon monoxide into the iridium-carbon bond.2. Highly selective cross [2+2+2] addition of two different monoynesHighly selective cross [2+2+2] addition of two different monoynes is achieved by using a catalytic amount of [Ir(cod)Cl]_2 and ligand. Ligand had a considerable effect on the reaction. When 1,2-bis(diphenylphosphino)ethane was used, two molecules of dimethyl acetylenedicarboxylate (DMAD) reacted with one molecule of a monoyne to give the 2:1 coupling product. When 1,2-bis(dipentafluorophenylphosphino)ethane was used instead of dppe, one molecule of DMAD reacted with two molecules of a monoyne to give the 1:2 coupling product.

对虹膜复合物催化反应的关注要少得多。该研究项目的目的是开发虹膜复合物催化的高度选择性反应。我们已经研究了大磷酸盐和交叉[2+2+2]的羰基化。将Allic磷酸盐[IR（COD）CL] _2的羰基化，诸如P（2-富度）_3，PPH_2C_6F_5或ASPH_3等配体的羰基化表现出较高的催化活性，用于在存在酒精的情况下将相应的磷酸盐的羰基化为相应的β，γ，γ，γ，γ-unsassaterated Estersers。在100℃的初始碳一氧化碳压力下，在100 kg/cm^2的初始碳（E）-4-苯基-3-丁烷酸乙基压力下，在ETOH的存在下，在ETOH存在下，苯基（E）-3-苯基-2-丙基磷酸的羰基化在90％的收益率上。获得NO（Z） - 异构体。在ETOH存在下2-烷基二乙基磷酸盐的羰基化产生了乙基（E） - （Z）-3-烷烯酸盐的混合物。在将碳一氧化碳插入虹膜碳键中之前，π-酰基虹膜中间体的同构异构化失去了起始材料的立体化学。2。高度选择性的交叉[2+2+2]添加了两个不同的monoynes高度选择性交叉[2+2+2]，通过使用催化量的[ir（cod）cl] _2和配体来实现两个不同的单体。配体对反应有很大影响。当使用1,2-双（二苯基苯基）乙烷时，两个分子的二甲基乙酰二酰基二羧酸酯（DMAD）与一个monoyne的一个分子反应，从而产生2：1耦合产物。当使用1,2-双（二苯基苯基）乙烷代替DPPE时，一个DMAD分子与两个monoyne的两个分子反应，从而产生1：2耦合产物。