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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.

铱配合物催化反应的研究较少。本课题的目的是开发铱配合物催化的高选择性反应。我们研究了烯丙位磷酸盐的羰基化反应以及两种不同单炔的交叉[2+2+2]环加成反应。1.烯丙基磷酸酯[Ir（cod）Cl]_2与配体P（2-呋喃基）_3、PPh_2C_6F_5或AsPh_3的羰基化反应对烯丙基磷酸酯在醇存在下的羰基化反应具有很高的催化活性。（E）-3-苯基-2-异丙烯基磷酸二乙酯在乙醇存在下于100℃、CO初始压力为40 kg/cm ^2的条件下进行羰基化反应，得到（E）-4-苯基-3-丁烯酸乙酯，产率90%。没有得到（Z）-异构体。2-烯基磷酸二乙酯在乙醇存在下羰基化得到（E）-和（Z）-3-烯酸乙酯的混合物。在将一氧化碳插入铱-碳键之前，通过π-烯丙基铱中间体的顺-反异构化失去了起始材料的立体化学。两种不同单炔的高选择性交叉[2 + 2 + 2]加成反应采用催化量的[Ir（cod）Cl]_2和配体实现了两种不同单炔的高选择性交叉[2+2+2]加成反应。配体对反应有很大的影响。当使用1，2-双（二苯基膦基）乙烷时，两分子乙炔二羧酸二甲酯（DMAD）与一分子单炔反应得到2：1偶联产物。当用1，2-双（二五氟苯基膦基）乙烷代替dppe时，一个DMAD分子与两个单炔分子反应得到1：2偶联产物。