Chemoselective and Enantioselective Oxidation of Indoles Employing Aspartyl Peptide Catalysts
Catalytic enantioselective indole oxidation is a process of particular relevance to the chemistry of complex alkaloids, as it has been implicated in their biosynthesis. In the context of synthetic methodology, catalytic enantioselective indole oxidation allows a rapid and biomimetic entry into sever...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society
2012
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| Online Access: | http://hdl.handle.net/1721.1/73591 https://orcid.org/0000-0003-3080-1063 |
| _version_ | 1826190352650862592 |
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| author | Movassaghi, Mohammad Noshi Alhanafy, Mohammad N. Tjandra, Meiliana Miller, Scott J. Kolundzic, Filip |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Movassaghi, Mohammad Noshi Alhanafy, Mohammad N. Tjandra, Meiliana Miller, Scott J. Kolundzic, Filip |
| author_sort | Movassaghi, Mohammad |
| collection | MIT |
| description | Catalytic enantioselective indole oxidation is a process of particular relevance to the chemistry of complex alkaloids, as it has been implicated in their biosynthesis. In the context of synthetic methodology, catalytic enantioselective indole oxidation allows a rapid and biomimetic entry into several classes of alkaloid natural products. Despite this potentially high utility in the total synthesis, reports of catalytic enantioselective indole oxidation remain sparse. Here we report a highly chemoselective catalytic system for the indole oxidation that delivers 3-hydroxy-indolenines with good chemical yields and moderate to high levels of enantio- and diastereoselectivity (up to 95:5 er and up to 92:8 dr). These results represent, to our knowledge, the most selective values yet reported in the literature for catalytic asymmetric indole oxidation. Furthermore, the utility of enantioenriched hydroxy-indolenines in stereospecific rearrangements is demonstrated. |
| first_indexed | 2024-09-23T08:38:46Z |
| format | Article |
| id | mit-1721.1/73591 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T08:38:46Z |
| publishDate | 2012 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/735912022-09-30T10:13:16Z Chemoselective and Enantioselective Oxidation of Indoles Employing Aspartyl Peptide Catalysts Movassaghi, Mohammad Noshi Alhanafy, Mohammad N. Tjandra, Meiliana Miller, Scott J. Kolundzic, Filip Massachusetts Institute of Technology. Department of Chemistry Movassaghi, Mohammad Movassaghi, Mohammad Noshi Alhanafy, Mohammad N. Tjandra, Meiliana Catalytic enantioselective indole oxidation is a process of particular relevance to the chemistry of complex alkaloids, as it has been implicated in their biosynthesis. In the context of synthetic methodology, catalytic enantioselective indole oxidation allows a rapid and biomimetic entry into several classes of alkaloid natural products. Despite this potentially high utility in the total synthesis, reports of catalytic enantioselective indole oxidation remain sparse. Here we report a highly chemoselective catalytic system for the indole oxidation that delivers 3-hydroxy-indolenines with good chemical yields and moderate to high levels of enantio- and diastereoselectivity (up to 95:5 er and up to 92:8 dr). These results represent, to our knowledge, the most selective values yet reported in the literature for catalytic asymmetric indole oxidation. Furthermore, the utility of enantioenriched hydroxy-indolenines in stereospecific rearrangements is demonstrated. National Institutes of Health (U.S.) and National Institute of General Medical Sciences (U.S.) (grant no. GM096403) National Institutes of Health (U.S.) and National Institute of General Medical Sciences (U.S.) (grant no. GM089732) Amgen, Inc. DuPont (Firm) 2012-10-04T13:44:44Z 2012-10-04T13:44:44Z 2011-05 2011-03 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/73591 Kolundzic, Filip et al. “Chemoselective and Enantioselective Oxidation of Indoles Employing Aspartyl Peptide Catalysts.” Journal of the American Chemical Society 133.23 (2011): 9104–9111. https://orcid.org/0000-0003-3080-1063 en_US http://dx.doi.org/10.1021/ja202706g 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 PMC |
| spellingShingle | Movassaghi, Mohammad Noshi Alhanafy, Mohammad N. Tjandra, Meiliana Miller, Scott J. Kolundzic, Filip Chemoselective and Enantioselective Oxidation of Indoles Employing Aspartyl Peptide Catalysts |
| title | Chemoselective and Enantioselective Oxidation of Indoles Employing Aspartyl Peptide Catalysts |
| title_full | Chemoselective and Enantioselective Oxidation of Indoles Employing Aspartyl Peptide Catalysts |
| title_fullStr | Chemoselective and Enantioselective Oxidation of Indoles Employing Aspartyl Peptide Catalysts |
| title_full_unstemmed | Chemoselective and Enantioselective Oxidation of Indoles Employing Aspartyl Peptide Catalysts |
| title_short | Chemoselective and Enantioselective Oxidation of Indoles Employing Aspartyl Peptide Catalysts |
| title_sort | chemoselective and enantioselective oxidation of indoles employing aspartyl peptide catalysts |
| url | http://hdl.handle.net/1721.1/73591 https://orcid.org/0000-0003-3080-1063 |
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