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铱催化亚联苯与烯烃的形式[4 + 1]环加成反应机理的密度泛函理论研究

DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes.

作者信息

Takano Hideaki, Sugimura Natsuhiko, Kanyiva Kyalo Stephen, Shibata Takanori

机构信息

Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Materials Characterization Central Laboratory, and International Center for Science and Engineering Program (ICSEP), Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 169-8555, Japan.

JST, ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan.

出版信息

ACS Omega. 2017 Aug 30;2(8):5228-5234. doi: 10.1021/acsomega.7b00403. eCollection 2017 Aug 31.

DOI:10.1021/acsomega.7b00403
PMID:31457794
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6641719/
Abstract

Recently, we reported an Ir-catalyzed formal [4 + 1] cycloaddition of biphenylenes with alkenes, which gave 9,9-disubstituted fluorenes in moderate to excellent yields. We proposed a reaction mechanism that involved the intermolecular insertion of alkenes, β-elimination, and intramolecular insertion based on the results of experimental mechanistic studies. Herein, we further support the proposed mechanism by density functional theory calculations and explain why [4 + 1] cycloaddition proceeds rather than conventional [4 + 2] cycloaddition.

摘要

最近，我们报道了铱催化的联亚苯基与烯烃的形式上的[4+1]环加成反应，该反应以中等至优异的产率得到9,9-二取代芴。基于实验机理研究的结果，我们提出了一种反应机理，该机理涉及烯烃的分子间插入、β-消除和分子内插入。在此，我们通过密度泛函理论计算进一步支持所提出的机理，并解释为什么发生[4+1]环加成而不是传统的[4+2]环加成。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/7778392f8c72/ao-2017-004032_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/42cae485f2a5/ao-2017-004032_0006.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/c526d4b778a6/ao-2017-004032_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/8a63175a87df/ao-2017-004032_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/5ab45ac093ca/ao-2017-004032_0003.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/947bfe3e305a/ao-2017-004032_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/7778392f8c72/ao-2017-004032_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/42cae485f2a5/ao-2017-004032_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/cae1cf5fa02b/ao-2017-004032_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/398a76c54bea/ao-2017-004032_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/c526d4b778a6/ao-2017-004032_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/8a63175a87df/ao-2017-004032_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/5ab45ac093ca/ao-2017-004032_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/dae6881cbb95/ao-2017-004032_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/947bfe3e305a/ao-2017-004032_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4ee7/6641719/7778392f8c72/ao-2017-004032_0005.jpg

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本文引用的文献

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