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基态二氧在环境条件下与丙二烯和亚硝基芳烃发生无金属的[3 + 2]环化反应。

Ground-state dioxygen undergoes metal-free [3 + 2]-annulations with allenes and nitrosoarenes under ambient conditions.

作者信息

Liu Jinxian, Skaria Manisha, Sharma Pankaj, Chiang Yun-Wei, Liu Rai-Shung

机构信息

Department of Chemistry , National Tsing-Hua University , Hsinchu , Taiwan , Republic of China . Email:

College of Chemistry & Materials Science , Longyan University , Fujian , China.

出版信息

Chem Sci. 2017 Aug 1;8(8):5482-5487. doi: 10.1039/c7sc01770g. Epub 2017 May 24.

DOI:10.1039/c7sc01770g
PMID:28970928
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5613744/
Abstract

The cycloadditions of molecular dioxygen with neutral π-bond motifs rely heavily on singlet-state O, whereas ground state O is chemically inactive. Here we report novel [3 + 2]-annulations among ground-state O (1 bar), allenes, and nitrosoarenes at low temperatures, efficiently yielding dioxygen-containing oxacycles. With less hindered 1-arylallene derivatives, these dioxygen species undergo skeletal rearrangement to 3-hydroxy-1-ketonyl-2-imine oxides. These cycloadditions represent valuable one-pot ,,-trifunctionalizations of allenes. Our EPR experiments confirm the presence of 1,4-diradical intermediates from an allene/nitrosoarene mixture, which manifest the hidden diradical properties of nitrosoarenes.

摘要

分子态双原子氧与中性π键基序的环加成反应严重依赖单重态氧，而基态氧在化学上是惰性的。在此，我们报道了在低温下基态氧（1巴）、丙二烯和亚硝基芳烃之间新型的[3 + 2]环化反应，能高效生成含双原子氧的氧杂环。对于位阻较小的1-芳基丙二烯衍生物，这些双原子氧物种会发生骨架重排，生成3-羟基-1-酮基-2-亚胺氧化物。这些环加成反应代表了丙二烯有价值的一锅法三官能团化反应。我们的电子顺磁共振实验证实了丙二烯/亚硝基芳烃混合物中存在1,4-双自由基中间体，这揭示了亚硝基芳烃隐藏的双自由基性质。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdad/5613744/b1f4e5461665/c7sc01770g-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdad/5613744/f5cdf5fcf0c1/c7sc01770g-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdad/5613744/042399408c9e/c7sc01770g-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdad/5613744/8f39c31cbfd8/c7sc01770g-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdad/5613744/b1f4e5461665/c7sc01770g-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdad/5613744/f5cdf5fcf0c1/c7sc01770g-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdad/5613744/042399408c9e/c7sc01770g-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdad/5613744/8f39c31cbfd8/c7sc01770g-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdad/5613744/b1f4e5461665/c7sc01770g-s2.jpg

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J Am Chem Soc. 2016 Aug 10;138(31):9763-6. doi: 10.1021/jacs.6b05216. Epub 2016 Jul 26.
2
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J Am Chem Soc. 2016 May 25;138(20):6416-9. doi: 10.1021/jacs.6b03931. Epub 2016 May 16.
3
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Org Lett. 2016 Feb 5;18(3):412-5. doi: 10.1021/acs.orglett.5b03447. Epub 2016 Jan 8.
4
Synthesis of Hindered α-Amino Carbonyls: Copper-Catalyzed Radical Addition with Nitroso Compounds.受阻α-氨基羰基的合成：铜催化的与亚硝基化合物的自由基加成反应。
J Am Chem Soc. 2015 Sep 16;137(36):11614-7. doi: 10.1021/jacs.5b07860. Epub 2015 Sep 2.
5
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6
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