Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions
Computational investigations of ligand-directed selectivities in Ullmann-type coupling reactions of methanol and methylamine with iodobenzene by β-diketone- and 1,10-phenanthroline-ligated CuI complexes are reported. Density functional theory calculations using several functionals were performed on...
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| Формат: | Статья |
| Язык: | en_US |
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American Chemical Society (ACS)
2012
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| Online-ссылка: | http://hdl.handle.net/1721.1/72018 https://orcid.org/0000-0003-1528-6438 https://orcid.org/0000-0003-3875-4775 |
| _version_ | 1826217817783926784 |
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| author | Buchwald, Stephen Leffler Jones, Gavin O. Houk, K. N. Liu, Peng |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Buchwald, Stephen Leffler Jones, Gavin O. Houk, K. N. Liu, Peng |
| author_sort | Buchwald, Stephen Leffler |
| collection | MIT |
| description | Computational investigations of ligand-directed selectivities in Ullmann-type coupling reactions of methanol and methylamine with iodobenzene by β-diketone- and 1,10-phenanthroline-ligated CuI complexes are reported. Density functional theory calculations using several functionals were performed on both the nucleophile formation and aryl halide activation steps of these reactions. The origin of ligand-directed selectivities in N- versus O-arylation reactions as described in a previous publication (J. Am. Chem. Soc. 2007, 129, 3490−3491) were studied and explained. The selectivities observed experimentally are derived not from initial CuI(nucleophile) complex formation but from the subsequent steps involving aryl halide activation. The arylation may occur via single-electron transfer (SET) or iodine atom transfer (IAT), depending on the electron-donating abilities of the ligand and nucleophile. Mechanisms involving either oxidative addition/reductive elimination or σ-bond metathesis are disfavored. SET mechanisms are favored in reactions promoted by the β-diketone ligand; N-arylation is predicted to be favored in these cases, in agreement with experimental results. The phenanthroline ligand promotes O-arylation reactions via IAT mechanisms in preference to N-arylation reactions, which occur via SET mechanisms; this result is also in agreement with experimental results. |
| first_indexed | 2024-09-23T17:09:38Z |
| format | Article |
| id | mit-1721.1/72018 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T17:09:38Z |
| publishDate | 2012 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/720182022-10-03T10:49:32Z Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions Buchwald, Stephen Leffler Jones, Gavin O. Houk, K. N. Liu, Peng Massachusetts Institute of Technology. Department of Chemistry Buchwald, Stephen L. Buchwald, Stephen Leffler Jones, Gavin O. Computational investigations of ligand-directed selectivities in Ullmann-type coupling reactions of methanol and methylamine with iodobenzene by β-diketone- and 1,10-phenanthroline-ligated CuI complexes are reported. Density functional theory calculations using several functionals were performed on both the nucleophile formation and aryl halide activation steps of these reactions. The origin of ligand-directed selectivities in N- versus O-arylation reactions as described in a previous publication (J. Am. Chem. Soc. 2007, 129, 3490−3491) were studied and explained. The selectivities observed experimentally are derived not from initial CuI(nucleophile) complex formation but from the subsequent steps involving aryl halide activation. The arylation may occur via single-electron transfer (SET) or iodine atom transfer (IAT), depending on the electron-donating abilities of the ligand and nucleophile. Mechanisms involving either oxidative addition/reductive elimination or σ-bond metathesis are disfavored. SET mechanisms are favored in reactions promoted by the β-diketone ligand; N-arylation is predicted to be favored in these cases, in agreement with experimental results. The phenanthroline ligand promotes O-arylation reactions via IAT mechanisms in preference to N-arylation reactions, which occur via SET mechanisms; this result is also in agreement with experimental results. National Institute of General Medical Sciences (U.S.) (grant no. GM-58160) National Institutes of Health (U.S.) (grant no. GM-36700) 2012-08-07T18:13:55Z 2012-08-07T18:13:55Z 2010-04 2010-01 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/72018 Buchwald, Stephen Leffler, et al. "Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions." Journal of the American Chemical Society 132.17 (2010): 6205–6213. Copyright © 2010 American Chemical Society https://orcid.org/0000-0003-1528-6438 https://orcid.org/0000-0003-3875-4775 en_US http://dx.doi.org/10.1021/ja100739h Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) PMC |
| spellingShingle | Buchwald, Stephen Leffler Jones, Gavin O. Houk, K. N. Liu, Peng Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions |
| title | Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions |
| title_full | Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions |
| title_fullStr | Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions |
| title_full_unstemmed | Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions |
| title_short | Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions |
| title_sort | computational explorations of mechanisms and ligand directed selectivities of copper catalyzed ullmann type reactions |
| url | http://hdl.handle.net/1721.1/72018 https://orcid.org/0000-0003-1528-6438 https://orcid.org/0000-0003-3875-4775 |
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