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烯丙基醚与芳基格氏试剂的交叉偶联反应在镍钳形配合物催化下进行。

Cross-Coupling Reaction of Allylic Ethers with Aryl Grignard Reagents Catalyzed by a Nickel Pincer Complex.

机构信息

Department of Advanced Materials Chemistry, Graduate School of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan.

出版信息

Molecules. 2019 Jun 21;24(12):2296. doi: 10.3390/molecules24122296.

DOI:10.3390/molecules24122296
PMID:31234296
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6631569/
Abstract

A cross-coupling reaction of allylic aryl ethers with arylmagnesium reagents was investigated using β-aminoketonato- and β-diketiminato-based pincer-type nickel(II) complexes as catalysts. An β-aminoketonato nickel(II) complex bearing a diphenylphosphino group as a third donor effectively catalyzed the reaction to afford the target cross-coupled products, allylbenzene derivatives, in high yield. The regioselective reaction of a variety of substituted cinnamyl ethers proceeded to give the corresponding linear products. In contrast, α- and γ-alkyl substituted allylic ethers afforded a mixture of the linear and branched products. These results indicated that the coupling reaction proceeded via a π-allyl nickel intermediate.

摘要

研究了烯丙基芳基醚与芳基镁试剂的交叉偶联反应,使用β-氨基酮酸盐和β-二酮亚胺基钳式镍(II)配合物作为催化剂。一个带有二苯基膦作为第三个给体的β-氨基酮酸盐镍(II)配合物有效地催化了反应,以高产率得到目标交叉偶联产物,烯丙基苯衍生物。各种取代肉桂基醚的区域选择性反应得到相应的线性产物。相比之下,α-和γ-烷基取代的烯丙基醚得到了线性和支化产物的混合物。这些结果表明,偶联反应通过π-烯丙基镍中间体进行。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9564/6631569/0620fa2dae6d/molecules-24-02296-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9564/6631569/b4ea297ca8f8/molecules-24-02296-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9564/6631569/74f65c98721c/molecules-24-02296-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9564/6631569/0620fa2dae6d/molecules-24-02296-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9564/6631569/b4ea297ca8f8/molecules-24-02296-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9564/6631569/74f65c98721c/molecules-24-02296-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9564/6631569/0620fa2dae6d/molecules-24-02296-sch003.jpg

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本文引用的文献

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