Aza Diels-Alder Reactions of Nitriles, N, N-Dimethylhydrazones, and Oximino Ethers. Application in Formal [2 + 2 + 2] Cycloadditions for the Synthesis of Pyridines
Metal-free, formal [2 + 2 + 2] cycloaddition st rategies for the synthesis of polycyclic pyridine derivatives are described. The overall transformation proceeds via a two-stage pericyclic cascade mechanism. In the first step, an intramolecular propargylic ene reaction generates a vinyl-allene that...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2018
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| Online Access: | http://hdl.handle.net/1721.1/119382 https://orcid.org/0000-0003-4681-8310 https://orcid.org/0000-0002-9812-206X |
| _version_ | 1826204606273683456 |
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| author | Hamzik, Philip Jonathan Goutierre, Anne-Sophie Sakai, Takeo Danheiser, Rick Lane |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Hamzik, Philip Jonathan Goutierre, Anne-Sophie Sakai, Takeo Danheiser, Rick Lane |
| author_sort | Hamzik, Philip Jonathan |
| collection | MIT |
| description | Metal-free, formal [2 + 2 + 2] cycloaddition st rategies for the synthesis of polycyclic pyridine derivatives are described. The overall transformation proceeds via a two-stage pericyclic cascade mechanism. In the first step, an intramolecular propargylic ene reaction generates a vinyl-allene that is necessarily locked in the s-cis conformation. This vinylallene exhibits exceptional reactivity as a Diels-Alder reaction partner and engages in [4 + 2] cycloadditions with normally unreactive aza dienophiles including unactivated cyano groups and heterosubstituted imine derivatives such as dimethylhydrazones and oximino ethers. Few examples of oximino ether Diels-Alder reactions have been reported previously and normal electron demand [4 + 2] cycloadditions of unactivated dialkylhydrazones are unprecedented. Overall this metal-free formal [2 + 2 + 2] cycloaddition provides access to polycyclic pyridine derivatives and complements transition metal-catalyzed [2 + 2 + 2] strategies. |
| first_indexed | 2024-09-23T12:58:07Z |
| format | Article |
| id | mit-1721.1/119382 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T12:58:07Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1193822022-10-01T12:14:10Z Aza Diels-Alder Reactions of Nitriles, N, N-Dimethylhydrazones, and Oximino Ethers. Application in Formal [2 + 2 + 2] Cycloadditions for the Synthesis of Pyridines Hamzik, Philip Jonathan Goutierre, Anne-Sophie Sakai, Takeo Danheiser, Rick Lane Massachusetts Institute of Technology. Department of Chemistry Danheiser, Rick Lane Hamzik, Philip Jonathan Goutierre, Anne-Sophie Sakai, Takeo Danheiser, Rick Lane Metal-free, formal [2 + 2 + 2] cycloaddition st rategies for the synthesis of polycyclic pyridine derivatives are described. The overall transformation proceeds via a two-stage pericyclic cascade mechanism. In the first step, an intramolecular propargylic ene reaction generates a vinyl-allene that is necessarily locked in the s-cis conformation. This vinylallene exhibits exceptional reactivity as a Diels-Alder reaction partner and engages in [4 + 2] cycloadditions with normally unreactive aza dienophiles including unactivated cyano groups and heterosubstituted imine derivatives such as dimethylhydrazones and oximino ethers. Few examples of oximino ether Diels-Alder reactions have been reported previously and normal electron demand [4 + 2] cycloadditions of unactivated dialkylhydrazones are unprecedented. Overall this metal-free formal [2 + 2 + 2] cycloaddition provides access to polycyclic pyridine derivatives and complements transition metal-catalyzed [2 + 2 + 2] strategies. National Science Foundation (U.S.) (CHE-1111567) National Science Foundation (U.S.) (CHE-1464799) Amgen Summer Graduate Fellowship Kenneth M. Gordon Summer Fellowship Japan Society for the Promotion of Science for Young Scientitists 2018-12-03T16:03:46Z 2018-12-03T16:03:46Z 2017-12 Article http://purl.org/eprint/type/JournalArticle 0022-3263 1520-6904 http://hdl.handle.net/1721.1/119382 Hamzik, Philip J., Anne-Sophie Goutierre, Takeo Sakai, and Rick L. Danheiser. “Aza Diels–Alder Reactions of Nitriles, N,N-Dimethylhydrazones, and Oximino Ethers. Application in Formal [2 + 2 + 2] Cycloadditions for the Synthesis of Pyridines.” The Journal of Organic Chemistry 82, no. 24 (December 2017): 12975–12991. https://orcid.org/0000-0003-4681-8310 https://orcid.org/0000-0002-9812-206X en_US http://dx.doi.org/10.1021/acs.joc.7b02503 The Journal of Organic Chemistry 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) Prof. Danheiser via Erja Kajosalo |
| spellingShingle | Hamzik, Philip Jonathan Goutierre, Anne-Sophie Sakai, Takeo Danheiser, Rick Lane Aza Diels-Alder Reactions of Nitriles, N, N-Dimethylhydrazones, and Oximino Ethers. Application in Formal [2 + 2 + 2] Cycloadditions for the Synthesis of Pyridines |
| title | Aza Diels-Alder Reactions of Nitriles, N, N-Dimethylhydrazones, and Oximino Ethers. Application in Formal [2 + 2 + 2] Cycloadditions for the Synthesis of Pyridines |
| title_full | Aza Diels-Alder Reactions of Nitriles, N, N-Dimethylhydrazones, and Oximino Ethers. Application in Formal [2 + 2 + 2] Cycloadditions for the Synthesis of Pyridines |
| title_fullStr | Aza Diels-Alder Reactions of Nitriles, N, N-Dimethylhydrazones, and Oximino Ethers. Application in Formal [2 + 2 + 2] Cycloadditions for the Synthesis of Pyridines |
| title_full_unstemmed | Aza Diels-Alder Reactions of Nitriles, N, N-Dimethylhydrazones, and Oximino Ethers. Application in Formal [2 + 2 + 2] Cycloadditions for the Synthesis of Pyridines |
| title_short | Aza Diels-Alder Reactions of Nitriles, N, N-Dimethylhydrazones, and Oximino Ethers. Application in Formal [2 + 2 + 2] Cycloadditions for the Synthesis of Pyridines |
| title_sort | aza diels alder reactions of nitriles n n dimethylhydrazones and oximino ethers application in formal 2 2 2 cycloadditions for the synthesis of pyridines |
| url | http://hdl.handle.net/1721.1/119382 https://orcid.org/0000-0003-4681-8310 https://orcid.org/0000-0002-9812-206X |
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