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Development of catalytic reactions via π-allyl iridium intermediate

π-烯丙基铱中间体催化反应的进展

基本信息

批准号：
12650857
负责人：
TAKEUCHI Ryo
金额：
$ 2.3万
依托单位：
Yokohama City University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2001
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12650857/
关键词：
iridium allylic amimation allylic alkylation regioselectivity allylic amine enynyl acetate π-allyl iridium solvent effect 立体選択性 π-アリル中間体

项目摘要

Iridium complexes have been used as a hydrogenation catalyst. Much less attention has been paid to iridium complex-catalyzed carbon-carbon bond formation. We first showed that [Ir(cod)Cl]_2/4P(Oph)_3 is an efficient catalyst for allylic alkylation. The reaction proceeds via π-allyl iridium intermediate, which is formed by oxidative addition of allylic esters to an iridium complex. The chemistry of π-allyl iridium intermediate should be useful for organic synthesis. The aim of this research project is to develop catalytic reactions via π-allyl iridium intermediate.1. Allylic animationWe found that an iridium complex is an efficient catalyst for allylic animation. The solvent strongly affected the catalytic activity. The use of a polar solvent such as EtOH is essential for obtaining the products in high yield. The reaction of (E)-3-substituted-2-propenyl carbonate and 1-substituted-2-propenyl carbonate with pyrrolidine in the presence of a catalytic amount of [Ir(cod)Cl]_2/4P(Oph)_3 gave … More a branched amine with up to 99 % selectivity. Both secondary and primary amines could be used. When a primary amine was used, selective monoallylation occurred. No diallylation product was obtained. The reaction of 1,1-disubstituted-2-propenyl acetate with amines exclusively gave an α,α-disubstituted allylic amine. This reaction provides an alternative route to the addition of an organometallic reagent to ketimines for preparation of such amines. The reaction of (Ζ)-3-substituted-2-propenyl carbonate with amines gave (Ζ)-linear amines with up to 100 % selectivity. In all cases, no (Ε)-linear amine was obtained. The selectivities described here have not been achieved in similar palladium complex-catalyzed reactions.2. Allylic alkylation of enynyl acetatesWe examined allylic alkylation of enynyl acetates. The reaction of 2-ethenyl-2-heptynyl acetate with diethyl sodiomalonate in the presence of a catalytic amount of [Ir(cod)Cl]_2 and P(Oet)_3 (P/Ir = 2) gave a branched product in 92 % selectivity. The reaction proceeds via 1-(1-alkynyl)-π-allyl iridium intermediate. We achieved a highly regioselective alkylation at 1-(1-alkynyl)-substituted allylic terminus. Less

Ir络合物已被用作加氢催化剂。而对Ir络合物催化的碳-碳键形成的研究则少之又少。我们首次证明了[Ir(Cod)Cl]_2/4P(OPh)_3是一种有效的烯丙基烷基化催化剂。反应通过π-烯丙基铱中间体进行，该中间体是由烯丙基酯氧化加成到Ir络合物上形成的。π-烯丙基Ir中间体的化学对有机合成具有重要的应用价值。本研究项目的目的是开发通过π-烯丙基Ir中间体的催化反应。烯丙基动画我们发现，铱的络合物是烯丙基动画的有效催化剂。溶剂对催化活性有很大影响。使用诸如乙醇等极性溶剂对于获得高产率的产品是必不可少的。(E)-3-取代-2-丙烯基碳酸酯和1-取代-2-丙烯基碳酸酯在催化量[Ir(Cod)Cl]_2/4P(OPh)_3存在下与吡咯烷反应生成…更多的是一种选择性高达99%的支化胺。仲胺和伯胺都可以使用。当使用伯胺时，发生选择性单烯丙基化。没有得到二烯丙化产物。1，1-二取代-2-丙烯基乙酸酯与胺反应得到α，α-二取代的烯丙基胺。该反应提供了将有机金属试剂加到酮胺以制备此类胺的另一种途径。(Ζ)-3-取代-2-丙烯基碳酸酯与胺反应生成(Ζ)-直线胺，选择性高达100%。在所有情况下，都没有得到(Ε)-直线胺。这里描述的选择性在类似的钯配合物催化的反应中是没有实现的。烯丙基乙酸酯的烯丙烷基化我们研究了烯丙基乙酸酯的烯丙基烷基化反应。在[Ir(Cod)Cl]_2和P(Oet)_3(P/Ir=2)催化下，2-乙烯基-2-庚炔基乙酸酯与二马来酸二乙酯反应生成支化产物，选择性达92%。反应通过1-(1-炔基)-π-烯丙基铱中间体进行。我们在1-(1-炔基)取代的烯丙基末端实现了高区域选择性的烷基化反应。较少