Theoretical Study on the Copper-Catalyzed <i>ortho</i>-Selective C-H Functionalization of Naphthols with <i>α</i>-Phenyl-<i>α</i>-Diazoesters
The aromatic C(sp<sup>2</sup>)-H functionalization of unprotected naphthols with <i>α</i>-phenyl-<i>α</i>-diazoesters under mild conditions catalyzed by CuCl and CuCl<sub>2</sub> exhibits high efficiency and unique <i>ortho</i>-selectivity....
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MDPI AG
2023-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/4/1767 |
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| author | Xiaoli Zhu Xunshen Liu Fei Xia Lu Liu |
| author_facet | Xiaoli Zhu Xunshen Liu Fei Xia Lu Liu |
| author_sort | Xiaoli Zhu |
| collection | DOAJ |
| description | The aromatic C(sp<sup>2</sup>)-H functionalization of unprotected naphthols with <i>α</i>-phenyl-<i>α</i>-diazoesters under mild conditions catalyzed by CuCl and CuCl<sub>2</sub> exhibits high efficiency and unique <i>ortho</i>-selectivity. In this study, the combination of density functional theory (DFT) calculations and experiments is employed to investigate the mechanism of C-H functionalization, which reveals the fundamental origin of the site-selectivity. It explains that CuCl-catalyzed <i>ortho</i>-selective C-H functionlization is due to the bimetallic carbene, which differs from the reaction catalyzed by CuCl<sub>2</sub> via monometallic carbene. The results demonstrate the function of favourable H-bond interactions on the site- and chemo-selectivity of reaction through stabilizing the rate-determining transition states in proton (1,3)-migration. |
| first_indexed | 2024-03-11T08:21:34Z |
| format | Article |
| id | doaj.art-fb86b726592d4a96913e91795cadfbf1 |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T08:21:34Z |
| publishDate | 2023-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-fb86b726592d4a96913e91795cadfbf12023-11-16T22:22:55ZengMDPI AGMolecules1420-30492023-02-01284176710.3390/molecules28041767Theoretical Study on the Copper-Catalyzed <i>ortho</i>-Selective C-H Functionalization of Naphthols with <i>α</i>-Phenyl-<i>α</i>-DiazoestersXiaoli Zhu0Xunshen Liu1Fei Xia2Lu Liu3School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai 200241, ChinaSchool of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai 200241, ChinaSchool of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai 200241, ChinaSchool of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai 200241, ChinaThe aromatic C(sp<sup>2</sup>)-H functionalization of unprotected naphthols with <i>α</i>-phenyl-<i>α</i>-diazoesters under mild conditions catalyzed by CuCl and CuCl<sub>2</sub> exhibits high efficiency and unique <i>ortho</i>-selectivity. In this study, the combination of density functional theory (DFT) calculations and experiments is employed to investigate the mechanism of C-H functionalization, which reveals the fundamental origin of the site-selectivity. It explains that CuCl-catalyzed <i>ortho</i>-selective C-H functionlization is due to the bimetallic carbene, which differs from the reaction catalyzed by CuCl<sub>2</sub> via monometallic carbene. The results demonstrate the function of favourable H-bond interactions on the site- and chemo-selectivity of reaction through stabilizing the rate-determining transition states in proton (1,3)-migration.https://www.mdpi.com/1420-3049/28/4/1767copper catalysis<i>ortho</i>-C(sp<sup>2</sup>)-H bond functionalizationnaphtholsdiazo compoundsmetal carbenedensity functional theory (DFT) calculations |
| spellingShingle | Xiaoli Zhu Xunshen Liu Fei Xia Lu Liu Theoretical Study on the Copper-Catalyzed <i>ortho</i>-Selective C-H Functionalization of Naphthols with <i>α</i>-Phenyl-<i>α</i>-Diazoesters Molecules copper catalysis <i>ortho</i>-C(sp<sup>2</sup>)-H bond functionalization naphthols diazo compounds metal carbene density functional theory (DFT) calculations |
| title | Theoretical Study on the Copper-Catalyzed <i>ortho</i>-Selective C-H Functionalization of Naphthols with <i>α</i>-Phenyl-<i>α</i>-Diazoesters |
| title_full | Theoretical Study on the Copper-Catalyzed <i>ortho</i>-Selective C-H Functionalization of Naphthols with <i>α</i>-Phenyl-<i>α</i>-Diazoesters |
| title_fullStr | Theoretical Study on the Copper-Catalyzed <i>ortho</i>-Selective C-H Functionalization of Naphthols with <i>α</i>-Phenyl-<i>α</i>-Diazoesters |
| title_full_unstemmed | Theoretical Study on the Copper-Catalyzed <i>ortho</i>-Selective C-H Functionalization of Naphthols with <i>α</i>-Phenyl-<i>α</i>-Diazoesters |
| title_short | Theoretical Study on the Copper-Catalyzed <i>ortho</i>-Selective C-H Functionalization of Naphthols with <i>α</i>-Phenyl-<i>α</i>-Diazoesters |
| title_sort | theoretical study on the copper catalyzed i ortho i selective c h functionalization of naphthols with i α i phenyl i α i diazoesters |
| topic | copper catalysis <i>ortho</i>-C(sp<sup>2</sup>)-H bond functionalization naphthols diazo compounds metal carbene density functional theory (DFT) calculations |
| url | https://www.mdpi.com/1420-3049/28/4/1767 |
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