Studying Regioisomer Formation in the Pd-Catalyzed Fluorination of Aryl Triflates by Deuterium Labeling
Isotopic labeling has been used to determine that a portion of the desired product in the Pd-catalyzed fluorination of electron-rich, non-ortho-substituted aryl triflates results from direct C–F cross-coupling. In some cases, formation of a Pd-aryne intermediate is responsible for producing undesire...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2015
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| Online Access: | http://hdl.handle.net/1721.1/99657 https://orcid.org/0000-0003-3875-4775 |
| _version_ | 1826206039671832576 |
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| author | Milner, Phillip John Kinzel, Tom Zhang, Yong Buchwald, Stephen Leffler |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Milner, Phillip John Kinzel, Tom Zhang, Yong Buchwald, Stephen Leffler |
| author_sort | Milner, Phillip John |
| collection | MIT |
| description | Isotopic labeling has been used to determine that a portion of the desired product in the Pd-catalyzed fluorination of electron-rich, non-ortho-substituted aryl triflates results from direct C–F cross-coupling. In some cases, formation of a Pd-aryne intermediate is responsible for producing undesired regioisomers. The generation of the Pd-aryne intermediate occurs primarily via ortho-deprotonation of a L·Pd(Ar)OTf (L = biaryl monophosphine) species by CsF and thus competes directly with the transmetalation step of the catalytic cycle. Deuterium labeling studies were conducted with a variety of aryl triflates. |
| first_indexed | 2024-09-23T13:23:03Z |
| format | Article |
| id | mit-1721.1/99657 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:23:03Z |
| publishDate | 2015 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/996572022-09-28T13:46:38Z Studying Regioisomer Formation in the Pd-Catalyzed Fluorination of Aryl Triflates by Deuterium Labeling Milner, Phillip John Kinzel, Tom Zhang, Yong Buchwald, Stephen Leffler Massachusetts Institute of Technology. Department of Chemistry Milner, Phillip John Kinzel, Tom Zhang, Yong Buchwald, Stephen Leffler Isotopic labeling has been used to determine that a portion of the desired product in the Pd-catalyzed fluorination of electron-rich, non-ortho-substituted aryl triflates results from direct C–F cross-coupling. In some cases, formation of a Pd-aryne intermediate is responsible for producing undesired regioisomers. The generation of the Pd-aryne intermediate occurs primarily via ortho-deprotonation of a L·Pd(Ar)OTf (L = biaryl monophosphine) species by CsF and thus competes directly with the transmetalation step of the catalytic cycle. Deuterium labeling studies were conducted with a variety of aryl triflates. National Institutes of Health (U.S.) (Award GM46059) National Science Foundation (U.S.) (Predoctoral Fellowship 2010094243) Amgen Inc. Alexander von Humboldt-Stiftung (Feodor Lynen Postdoctoral Fellowship) 2015-11-02T18:49:21Z 2015-11-02T18:49:21Z 2014-10 2014-09 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/99657 Milner, Phillip J., Tom Kinzel, Yong Zhang, and Stephen L. Buchwald. “Studying Regioisomer Formation in the Pd-Catalyzed Fluorination of Aryl Triflates by Deuterium Labeling.” Journal of the American Chemical Society 136, no. 44 (November 5, 2014): 15757–15766. © 2014 American Chemical Society https://orcid.org/0000-0003-3875-4775 en_US http://dx.doi.org/10.1021/ja509144r 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) ACS |
| spellingShingle | Milner, Phillip John Kinzel, Tom Zhang, Yong Buchwald, Stephen Leffler Studying Regioisomer Formation in the Pd-Catalyzed Fluorination of Aryl Triflates by Deuterium Labeling |
| title | Studying Regioisomer Formation in the Pd-Catalyzed Fluorination of Aryl Triflates by Deuterium Labeling |
| title_full | Studying Regioisomer Formation in the Pd-Catalyzed Fluorination of Aryl Triflates by Deuterium Labeling |
| title_fullStr | Studying Regioisomer Formation in the Pd-Catalyzed Fluorination of Aryl Triflates by Deuterium Labeling |
| title_full_unstemmed | Studying Regioisomer Formation in the Pd-Catalyzed Fluorination of Aryl Triflates by Deuterium Labeling |
| title_short | Studying Regioisomer Formation in the Pd-Catalyzed Fluorination of Aryl Triflates by Deuterium Labeling |
| title_sort | studying regioisomer formation in the pd catalyzed fluorination of aryl triflates by deuterium labeling |
| url | http://hdl.handle.net/1721.1/99657 https://orcid.org/0000-0003-3875-4775 |
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