Ti-Catalyzed Straightforward Synthesis of Exocyclic Allenes
Exocyclic allenes constitute useful building blocks in organic synthesis and have recently been identified as key intermediates in the synthesis of natural products. Here the first general method for the most straightforward synthesis of exocyclic allenes reported to date is presented. This method...
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| Format: | info:eu-repo/semantics/article |
| Language: | English |
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Wiley
2023
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| Online Access: | http://hdl.handle.net/10835/14712 https://doi.org/10.1002/chem.201304033 |
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| author | Muñoz-Gascón, Juan Hernández Cervantes, Carmen Padial, Natalia M. Álvarez Corral, Míriam Rosales Martínez, Antonio Rodríguez García, Ignacio Manuel Oltra, J. Enrique |
| author_facet | Muñoz-Gascón, Juan Hernández Cervantes, Carmen Padial, Natalia M. Álvarez Corral, Míriam Rosales Martínez, Antonio Rodríguez García, Ignacio Manuel Oltra, J. Enrique |
| author_sort | Muñoz-Gascón, Juan |
| collection | DSpace |
| description | Exocyclic allenes constitute useful building blocks in organic synthesis and have recently been identified as key
intermediates in the synthesis of natural products. Here the first general method for the most straightforward synthesis of exocyclic allenes reported to date is presented. This method is based on the Barbier-type cyclization of propargyl halides catalyzed by titanium; a safe, abundant, and ecofriendly metal. The reaction proceeds under mild conditions compatible with different functional groups and provides good yields of five-, six-, and seven-membered carbocycles and nitrogen-containing heterocycles bearing an exocyclic allene group. Experimental evidence supporting the proposed reaction mechanism is also provided. Moreover, this procedure can be carried out in an enantioselective manner by using chiral titanocene(III) catalysts. The utility of this method has been proved in the synthesis of the natural alkaloid stemoamide. |
| format | info:eu-repo/semantics/article |
| id | oai:repositorio.ual.es:10835-14712 |
| institution | Universidad de Cuenca |
| language | English |
| publishDate | 2023 |
| publisher | Wiley |
| record_format | dspace |
| spelling | oai:repositorio.ual.es:10835-147122023-12-04T07:23:17Z Ti-Catalyzed Straightforward Synthesis of Exocyclic Allenes Muñoz-Gascón, Juan Hernández Cervantes, Carmen Padial, Natalia M. Álvarez Corral, Míriam Rosales Martínez, Antonio Rodríguez García, Ignacio Manuel Oltra, J. Enrique Organic Chemistry Exocyclic allenes constitute useful building blocks in organic synthesis and have recently been identified as key intermediates in the synthesis of natural products. Here the first general method for the most straightforward synthesis of exocyclic allenes reported to date is presented. This method is based on the Barbier-type cyclization of propargyl halides catalyzed by titanium; a safe, abundant, and ecofriendly metal. The reaction proceeds under mild conditions compatible with different functional groups and provides good yields of five-, six-, and seven-membered carbocycles and nitrogen-containing heterocycles bearing an exocyclic allene group. Experimental evidence supporting the proposed reaction mechanism is also provided. Moreover, this procedure can be carried out in an enantioselective manner by using chiral titanocene(III) catalysts. The utility of this method has been proved in the synthesis of the natural alkaloid stemoamide. 2023-12-04T07:23:17Z 2023-12-04T07:23:17Z 2014-01-13 info:eu-repo/semantics/article Chem. Eur. J., 2014, 20: 801-810 http://hdl.handle.net/10835/14712 https://doi.org/10.1002/chem.201304033 en https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.201304033 info:eu-repo/semantics/openAccess Wiley This is Wiley-VCH – CTA – DE – Phys Sci – EN – the accepted version of the following article: Muñoz-Bascón, J., Hernández-Cervantes, C., Padial, N.M., Álvarez-Corral, M., Rosales, A., Rodríguez-García, I. and Oltra, J.E.“Ti-Catalyzed Straightforward Synthesis of Exocyclic Allenes“ Chem. Eur. J., 2014, 20: 801-810, which has been published in final form at [https://doi.org/10.1002/chem.201304033]. This article may be used for non-commercial purposes in accordance with the Wiley Self-Archiving Policy [https://authorservices.wiley.com/authorresources/Journal-Authors/licensing/self-archiving.html]. |
| spellingShingle | Organic Chemistry Muñoz-Gascón, Juan Hernández Cervantes, Carmen Padial, Natalia M. Álvarez Corral, Míriam Rosales Martínez, Antonio Rodríguez García, Ignacio Manuel Oltra, J. Enrique Ti-Catalyzed Straightforward Synthesis of Exocyclic Allenes |
| title | Ti-Catalyzed Straightforward Synthesis of Exocyclic Allenes |
| title_full | Ti-Catalyzed Straightforward Synthesis of Exocyclic Allenes |
| title_fullStr | Ti-Catalyzed Straightforward Synthesis of Exocyclic Allenes |
| title_full_unstemmed | Ti-Catalyzed Straightforward Synthesis of Exocyclic Allenes |
| title_short | Ti-Catalyzed Straightforward Synthesis of Exocyclic Allenes |
| title_sort | ti-catalyzed straightforward synthesis of exocyclic allenes |
| topic | Organic Chemistry |
| url | http://hdl.handle.net/10835/14712 https://doi.org/10.1002/chem.201304033 |
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