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

虹膜络合物催化剂。中间体应该对有机合成有用。活性。 f催化量的[IR（COD）CL] _2/4p（OPH）_3产生了更多的分支胺，最多可获得99％的选择性。 2-丙肾上腺素给出了α-二取代的盟友，以供酮酮的酮酮与酮的反应。在此处描述的所有cass中的选择性尚未在类似的钯型催化反应中实现。2在存在催化量的[ir（cod）_2] _2 _2 _2的情况下，Enynyl乙酸的烯基烷基化烯烷基化P（oet）_3（p/ir = 2）在1-（1-allkynyl） - 取代的Allyliclic末端下的分支机构的分支