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.

对铱络合物催化反应的关注较少。本研究项目的目的是开发铱络合物催化的高选择性反应，我们研究了烯丙基磷酸酯的羰基化和两者的交叉[2+2+2]环加成反应。不同的单炔。1. 烯丙基磷酸酯[Ir(cod)Cl]_2与配体如P(2-呋喃基)_3的羰基化， PPh_2C_6F_5 或 AsPh_3 在醇存在下对烯丙磷酸酯的羰基化反应生成相应的 β,γ-不饱和酯具有较高的催化活性。在100℃、40 kg/cm^2 初始一氧化碳压力下得到乙基得到(E)-4-苯基-3-丁烯酸酯，收率为90%。在EtOH存在下，2-链烯基二乙基磷酸酯的羰基化得到乙基(E)-和(Z)-异构体。 )-3-链烯酸酯在插入一氧化碳之前通过π-烯丙基铱中间体的顺反异构化而损失。 2. 两种不同单炔的高选择性交叉 [2+2+2] 加成通过使用催化量的 [Ir(cod) 实现两种不同单炔的高选择性交叉 [2+2+2] 加成)Cl]_2 和配体对反应有相当大的影响。乙炔二羧酸酯 (DMAD) 与一分子单炔反应生成 2:1 偶联产物当使用 1,2-双(二五氟苯基膦)乙烷代替 dppe 时，一分子 DMAD 与两分子单炔反应生成 2:1 偶联产物。 1:2耦合产品。