Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles
We report a highly enantioselective CuH-catalyzed Markovnikov hydrosilylation of vinylarenes and vinyl heterocycles. This method has a broad scope and enables both the synthesis of isolable silanes and the conversion of crude products to chiral alcohols. Density functional theory calculations suppor...
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| Format: | Article |
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American Chemical Society (ACS)
2018
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| Online Access: | http://hdl.handle.net/1721.1/113039 https://orcid.org/0000-0003-2008-3264 https://orcid.org/0000-0002-7896-1683 https://orcid.org/0000-0001-5418-3082 https://orcid.org/0000-0003-3875-4775 |
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| author | Gribble, Michael William Pirnot, Michael T Bandar, Jeffrey Liu, Richard Buchwald, Stephen Leffler |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Gribble, Michael William Pirnot, Michael T Bandar, Jeffrey Liu, Richard Buchwald, Stephen Leffler |
| author_sort | Gribble, Michael William |
| collection | MIT |
| description | We report a highly enantioselective CuH-catalyzed Markovnikov hydrosilylation of vinylarenes and vinyl heterocycles. This method has a broad scope and enables both the synthesis of isolable silanes and the conversion of crude products to chiral alcohols. Density functional theory calculations support a mechanism proceeding by hydrocupration followed by σ-bond metathesis with a hydrosilane. |
| first_indexed | 2024-09-23T15:17:27Z |
| format | Article |
| id | mit-1721.1/113039 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T15:17:27Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1130392022-10-02T01:57:59Z Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles Gribble, Michael William Pirnot, Michael T Bandar, Jeffrey Liu, Richard Buchwald, Stephen Leffler Massachusetts Institute of Technology. Department of Chemistry Gribble, Michael William Pirnot, Michael T Bandar, Jeffrey Liu, Richard Buchwald, Stephen Leffler We report a highly enantioselective CuH-catalyzed Markovnikov hydrosilylation of vinylarenes and vinyl heterocycles. This method has a broad scope and enables both the synthesis of isolable silanes and the conversion of crude products to chiral alcohols. Density functional theory calculations support a mechanism proceeding by hydrocupration followed by σ-bond metathesis with a hydrosilane. National Institutes of Health (U.S.) (Award GM46059) National Institutes of Health (U.S.) (Postdoctoral Fellowship 1F32GM113311) National Institutes of Health (U.S.) (Postdoctoral Fellowship GM112197) 2018-01-10T15:41:53Z 2018-01-10T15:41:53Z 2017-01 2016-12 2018-01-09T18:43:28Z Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/113039 Gribble, Michael W., et al. “Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles.” Journal of the American Chemical Society, vol. 139, no. 6, Feb. 2017, pp. 2192–95. © 2017 American Chemical Society. https://orcid.org/0000-0003-2008-3264 https://orcid.org/0000-0002-7896-1683 https://orcid.org/0000-0001-5418-3082 https://orcid.org/0000-0003-3875-4775 http://dx.doi.org/10.1021/JACS.6B13029 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 | Gribble, Michael William Pirnot, Michael T Bandar, Jeffrey Liu, Richard Buchwald, Stephen Leffler Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles |
| title | Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles |
| title_full | Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles |
| title_fullStr | Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles |
| title_full_unstemmed | Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles |
| title_short | Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles |
| title_sort | asymmetric copper hydride catalyzed markovnikov hydrosilylation of vinylarenes and vinyl heterocycles |
| url | http://hdl.handle.net/1721.1/113039 https://orcid.org/0000-0003-2008-3264 https://orcid.org/0000-0002-7896-1683 https://orcid.org/0000-0001-5418-3082 https://orcid.org/0000-0003-3875-4775 |
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