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

铱配合物已被用作氢化催化剂，但人们对铱配合物催化的碳-碳键形成的关注较少。我们首先表明[Ir(cod)Cl]_2/4P(Oph)_3是一种有效的催化剂。烯丙基烷基化反应通过π-烯丙基铱中间体进行，该中间体是通过将烯丙酯氧化加成到铱络合物上而形成的。铱中间体应可用于有机合成。该研究项目的目的是通过π-烯丙基铱中间体开发强催化反应。1．烯丙基动画我们发现铱配合物是烯丙基动画的有效催化剂。 (E)-3-取代-2-丙烯基碳酸酯的反应需要使用极性溶剂（例如 EtOH）来获得高产率的产物。 1-取代-2-丙烯基碳酸酯与吡咯烷在催化量的 [Ir(cod)Cl]_2/4P(Oph)_3 存在下生成仲胺和伯胺选择性高达 99% 的支链胺。当使用伯胺时，没有发生选择性单烯丙基化反应。 1,1-二取代-2-丙烯基乙酸酯与胺专门生成α,α-二取代烯丙胺。该反应提供了将有机金属试剂添加到酮亚胺中以制备此类胺的替代途径。碳酸-3-取代-2-丙烯基酯与胺生成(Z)-直链胺，In选择性高达100%。在所有情况下，均未获得(E)-直链胺。在类似的钯络合物催化反应中尚未实现本文所述的选择性。 2.乙酸烯炔酯的烯丙基烷基化我们研究了乙酸烯炔酯的烯丙基烷基化反应。乙酸 2-庚炔酯与丙二酸二乙酯在催化量的存在下反应[Ir(cod)Cl]_2 和 P(Oet)_3 (P/Ir = 2) 以 92% 的选择性产生支化产物。该反应通过 1-(1-炔基)-π-烯丙基铱中间体进行。在 1-(1-炔基)-取代的烯丙基末端进行高度区域选择性烷基化。