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Oxidative Cyclization on Nickel (0) Complexes having Bulky Ligand

具有大配体的镍 (0) 配合物的氧化环化

基本信息

批准号：
18350051
负责人：
OGOSHI Sensuke
金额：
$ 11.14万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18350051/
关键词：
Oxidative cyclization Nickel [2+2+2] Cycloaddition Alkyne Aldehyde Imine

项目摘要

We demonstrated that the oxidative cyclization of an imine and an alkyne on nickel (0) proceeded quantitatively to give a five-membered aza-nickelacycle, nickelapyrroline, and the insertion of the second alkyne to give a seven-membered aza-nickelacycle, nickeladihydroazepine, for the first time. We also reported that the reductive elimination from the nickeladihydroazepine led to the formation of 1,2-dihydropyridine. Moreover, this sequential reaction process was expanded to a nickel-catalyzed [2+2+2] cycloaddition of two alkynes and an imine to synthesize a 1,2-dihydropyridine. This reaction is the first example of the selective formation of 1,2-dihydropyridine by a transition metal-catalyzed reaction.The formation of a five-membered oxa-nickelacycle, nickeladihydrofuran, by oxidative cyclization of an alkyne and an aldehyde with nickel (0) was demonstrated for the first time. Moreover, we also demonstrated the transformation of the nickeladihydrofuran into an enone by decomposition, a lactone by carbonylation and an allylic alcohol by treatment with ZnMe_2, which suggests that nickeladihydrofuran is an important intermediate in a variety of catalytic reactions. As an example of oxidative cyclization of a carbonyl group and an alkyne with nickel (0), the reaction of carbon dioxiside and an alkyne with nickel (0) to give a nickelalactone had been reported. Although it is very important work in this field, the nickelalactone can not act as a key inetermediate in mutlicomponent coupling reactions as well as hydroacylation reactions.

我们首次证明了亚胺和炔在镍(0)上的氧化环化得到五元叠氮-镍环，镍吡咯啉，第二个炔的插入得到七元叠氮-镍环，镍二氢氮卓。我们还报道了镍二氢氮平的还原消除导致1,2-二氢吡啶的形成。此外，该顺序反应过程扩展为镍催化的两个炔和一个亚胺的[2+2+2]环加成反应，合成1,2-二氢吡啶。这个反应是第一个由过渡金属催化反应选择性生成1,2-二氢吡啶的例子。首次证实了炔和醛与镍(0)的氧化环化反应生成五元氧-镍环二氢呋喃。此外，我们还证明了二氢呋喃镍通过分解转化为烯酮，通过羰基化转化为内酯，通过ZnMe_2处理转化为烯丙醇，这表明二氢呋喃镍是多种催化反应的重要中间体。作为羰基和炔与镍(0)氧化环化的一个例子，已报道了二氧化碳和炔与镍(0)反应生成镍内酯。虽然镍内酯在这一领域的研究非常重要，但在多组分偶联反应和氢酰化反应中，镍内酯不能作为关键中间体。