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金催化的互补硝基炔内部氧化还原过程:一项密度泛函理论研究

Gold-Catalyzed Complementary Nitroalkyne Internal Redox Process: A DFT Study.

作者信息

Vipin Raj K, Dhote Pawan S, Vanka Kumar, Ramana Chepuri V

机构信息

Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, Pune, India.

Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, India.

出版信息

Front Chem. 2021 Jul 9;9:689780. doi: 10.3389/fchem.2021.689780. eCollection 2021.

DOI:10.3389/fchem.2021.689780
PMID:34307296
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8299333/
Abstract

Gold-catalysis, in this century, is one of the most emerging and promising new areas of research in organic synthesis. During the last two decades, a wide range of distinct synthetic methodologies have been unveiled employing homogeneous gold catalysis and aptly applied in the synthesis of numerous natural products and biologically active molecules. Among these, the reactions involving α-oxo gold carbene/α-imino gold carbene intermediates are of contemporary interest, in view of their synthetic potential and also due to the need to understand the bonding involved in these complexes. In this manuscript, we document the theoretical investigations on the regio-selectivity dependence of substitution on the gold-catalyzed cycloisomerization of -nitroarylalkyne derivatives. We have also studied the relative stabilities of α-oxo gold carbene intermediates.

摘要

在本世纪,金催化是有机合成中最具新兴性和前景的研究新领域之一。在过去二十年中,已揭示出多种不同的合成方法,这些方法采用均相金催化,并恰当地应用于众多天然产物和生物活性分子的合成。其中,涉及α-氧代金卡宾/α-亚胺基金卡宾中间体的反应因其合成潜力以及理解这些配合物中键合的必要性而备受当代关注。在本手稿中,我们记录了关于取代基的区域选择性对金催化的硝基芳基炔烃衍生物环异构化的影响的理论研究。我们还研究了α-氧代金卡宾中间体的相对稳定性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1429/8299333/18ee192a4a0f/fchem-09-689780-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1429/8299333/10073b00dc5b/fchem-09-689780-fx1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1429/8299333/2546112c4e4f/fchem-09-689780-fx2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1429/8299333/18ee192a4a0f/fchem-09-689780-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1429/8299333/10073b00dc5b/fchem-09-689780-fx1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1429/8299333/2546112c4e4f/fchem-09-689780-fx2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1429/8299333/18ee192a4a0f/fchem-09-689780-g001.jpg

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本文引用的文献

1
Nitrene Transfer and Carbene Transfer in Gold Catalysis.金催化中的氮烯转移和卡宾转移。
Chem Rev. 2021 Jul 28;121(14):9039-9112. doi: 10.1021/acs.chemrev.0c00348. Epub 2020 Aug 3.
2
Gold catalysis in total synthesis - recent achievements.金催化在全合成中的应用——最新进展。
Chem Soc Rev. 2016 Mar 7;45(5):1331-67. doi: 10.1039/c5cs00721f.
3
Catalytic access to α-oxo gold carbenes by N-O bond oxidants.通过 N-O 键氧化剂实现α-氧代金卡宾的催化途径。
Acc Chem Res. 2014 Mar 18;47(3):966-77. doi: 10.1021/ar4001839. Epub 2014 Feb 11.
4
A non-diazo approach to α-oxo gold carbenes via gold-catalyzed alkyne oxidation.一种通过金催化炔烃氧化制备α-氧代金卡宾的非重氮方法。
Acc Chem Res. 2014 Mar 18;47(3):877-88. doi: 10.1021/ar400181x. Epub 2014 Jan 15.
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1,6-Carbene transfer: gold-catalyzed oxidative diyne cyclizations.1,6-卡宾转移:金催化的氧化二炔环化反应。
J Am Chem Soc. 2013 Oct 16;135(41):15662-6. doi: 10.1021/ja4085385. Epub 2013 Oct 4.
6
[3,3]-Sigmatropic rearrangement versus carbene formation in gold-catalyzed transformations of alkynyl aryl sulfoxides: mechanistic studies and expanded reaction scope.金催化炔基芳基砜化合物转化中的[3,3]-σ重排与卡宾形成反应:机理研究及扩展的反应范围。
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Gold- and iodine-mediated internal oxygen transfer of nitrone- and sulfoxide-functionalized alkynes.金和碘介导的硝酮和亚砜官能化炔烃的内部氧转移。
J Org Chem. 2011 Oct 21;76(20):8488-94. doi: 10.1021/jo201347r. Epub 2011 Sep 20.
8
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10
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