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Metal‐Free Temperature‐Controlled Regiodivergent Borylative Cyclizations of Enynes: BCl(3)‐Promoted Skeletal Rearrangement
Metal‐free borylative cyclization of biphenyl‐embedded 1,3,5‐trien‐7‐ynes in the presence of simple and inexpensive BCl(3) provided synthetically useful borylated building blocks. The outcome of the process depends on the reaction temperature, with borylated phenanthrenes obtained at 60 °C and phena...
| Autores principales: | , , , , |
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| Formato: | Online Artículo Texto |
| Lenguaje: | English |
| Publicado: |
John Wiley and Sons Inc.
2022
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| Materias: | |
| Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9401584/ https://www.ncbi.nlm.nih.gov/pubmed/35510716 http://dx.doi.org/10.1002/anie.202205651 |
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| author | Milián, Ana Fernández‐Rodríguez, Manuel A. Merino, Estíbaliz Vaquero, Juan J. García‐García, Patricia |
| author_facet | Milián, Ana Fernández‐Rodríguez, Manuel A. Merino, Estíbaliz Vaquero, Juan J. García‐García, Patricia |
| author_sort | Milián, Ana |
| collection | PubMed |
| description | Metal‐free borylative cyclization of biphenyl‐embedded 1,3,5‐trien‐7‐ynes in the presence of simple and inexpensive BCl(3) provided synthetically useful borylated building blocks. The outcome of the process depends on the reaction temperature, with borylated phenanthrenes obtained at 60 °C and phenanthrene‐fused borylated cyclobutanes formed at 0 °C. Based on DFT calculations, a mechanism for these novel transformations has been proposed, which involves an uncommon skeletal rearrangement, including migration of a methyl group and alkyne fragmentation, unprecedented in BCl(3)‐promoted cyclization reactions. |
| format | Online Article Text |
| id | pubmed-9401584 |
| institution | National Center for Biotechnology Information |
| language | English |
| publishDate | 2022 |
| publisher | John Wiley and Sons Inc. |
| record_format | MEDLINE/PubMed |
| spelling | pubmed-94015842022-08-26 Metal‐Free Temperature‐Controlled Regiodivergent Borylative Cyclizations of Enynes: BCl(3)‐Promoted Skeletal Rearrangement Milián, Ana Fernández‐Rodríguez, Manuel A. Merino, Estíbaliz Vaquero, Juan J. García‐García, Patricia Angew Chem Int Ed Engl Communications Metal‐free borylative cyclization of biphenyl‐embedded 1,3,5‐trien‐7‐ynes in the presence of simple and inexpensive BCl(3) provided synthetically useful borylated building blocks. The outcome of the process depends on the reaction temperature, with borylated phenanthrenes obtained at 60 °C and phenanthrene‐fused borylated cyclobutanes formed at 0 °C. Based on DFT calculations, a mechanism for these novel transformations has been proposed, which involves an uncommon skeletal rearrangement, including migration of a methyl group and alkyne fragmentation, unprecedented in BCl(3)‐promoted cyclization reactions. John Wiley and Sons Inc. 2022-05-24 2022-07-11 /pmc/articles/PMC9401584/ /pubmed/35510716 http://dx.doi.org/10.1002/anie.202205651 Text en © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made. |
| spellingShingle | Communications Milián, Ana Fernández‐Rodríguez, Manuel A. Merino, Estíbaliz Vaquero, Juan J. García‐García, Patricia Metal‐Free Temperature‐Controlled Regiodivergent Borylative Cyclizations of Enynes: BCl(3)‐Promoted Skeletal Rearrangement |
| title | Metal‐Free Temperature‐Controlled Regiodivergent Borylative Cyclizations of Enynes: BCl(3)‐Promoted Skeletal Rearrangement |
| title_full | Metal‐Free Temperature‐Controlled Regiodivergent Borylative Cyclizations of Enynes: BCl(3)‐Promoted Skeletal Rearrangement |
| title_fullStr | Metal‐Free Temperature‐Controlled Regiodivergent Borylative Cyclizations of Enynes: BCl(3)‐Promoted Skeletal Rearrangement |
| title_full_unstemmed | Metal‐Free Temperature‐Controlled Regiodivergent Borylative Cyclizations of Enynes: BCl(3)‐Promoted Skeletal Rearrangement |
| title_short | Metal‐Free Temperature‐Controlled Regiodivergent Borylative Cyclizations of Enynes: BCl(3)‐Promoted Skeletal Rearrangement |
| title_sort | metal‐free temperature‐controlled regiodivergent borylative cyclizations of enynes: bcl(3)‐promoted skeletal rearrangement |
| topic | Communications |
| url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9401584/ https://www.ncbi.nlm.nih.gov/pubmed/35510716 http://dx.doi.org/10.1002/anie.202205651 |
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