Stereodefined polymetalloid alkenes synthesis via stereoselective boron-masking of polyborylated alkenes
Abstract Polyborylated-alkenes are valuable polymetalloid reagents in modern organic synthesis, providing access to a wide array of transformations, including the construction of multiple C–C and C–heteroatom bonds. However, because they contain similar boryl groups, many times their transformation...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2023-04-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-37733-0 |
| _version_ | 1797845916468641792 |
|---|---|
| author | Nadim Eghbarieh Nicole Hanania Ahmad Masarwa |
| author_facet | Nadim Eghbarieh Nicole Hanania Ahmad Masarwa |
| author_sort | Nadim Eghbarieh |
| collection | DOAJ |
| description | Abstract Polyborylated-alkenes are valuable polymetalloid reagents in modern organic synthesis, providing access to a wide array of transformations, including the construction of multiple C–C and C–heteroatom bonds. However, because they contain similar boryl groups, many times their transformation faces the main challenge in controlling the chemo-, regio- and stereoselectivity. One way to overcome these limitations is by installing different boron groups that can provide an opportunity to tune their reactivity toward better chemo-, regio- and stereoselectivity. Yet, the preparation of polyborylated-alkenes containing different boryl groups has been rare. Herein we report concise, highly site-selective, and stereoselective boron-masking strategies of polyborylated alkenes. This is achieved by designed stereoselective trifluorination and MIDA-ation reactions of readily available starting polyborylated alkenes. Additionally, the trifluoroborylated-alkenes undergo a stereospecific interconversion to Bdan-alkenes. These transition-metal free reactions provide a general and efficient method for the conversion of polyborylated alkenes to access 1,1-di-, 1,2-di-, 1,1,2-tris-(borylated) alkenes containing BF3M, Bdan, and BMIDA, a family of compounds that currently lack efficient synthetic access. Moreover, tetraborylethene undergoes the metal-free MIDA-ation reaction to provide the mono BMIDA tetraboryl alkene selectively. The mixed polyborylalkenes are then demonstrated to be useful in selective C–C and C–heteroatom bond-forming reactions. Given its simplicity and versatility, these stereoselective boron-masking approaches hold great promise for organoboron synthesis and will result in more transformations. |
| first_indexed | 2024-04-09T17:46:41Z |
| format | Article |
| id | doaj.art-fed569e718754d7791187cb0ab6750e6 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-04-09T17:46:41Z |
| publishDate | 2023-04-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-fed569e718754d7791187cb0ab6750e62023-04-16T11:18:09ZengNature PortfolioNature Communications2041-17232023-04-0114111110.1038/s41467-023-37733-0Stereodefined polymetalloid alkenes synthesis via stereoselective boron-masking of polyborylated alkenesNadim Eghbarieh0Nicole Hanania1Ahmad Masarwa2Institute of Chemistry, The Center for Nanoscience and Nanotechnology, Casali Center for Applied Chemistry, The Hebrew University of JerusalemInstitute of Chemistry, The Center for Nanoscience and Nanotechnology, Casali Center for Applied Chemistry, The Hebrew University of JerusalemInstitute of Chemistry, The Center for Nanoscience and Nanotechnology, Casali Center for Applied Chemistry, The Hebrew University of JerusalemAbstract Polyborylated-alkenes are valuable polymetalloid reagents in modern organic synthesis, providing access to a wide array of transformations, including the construction of multiple C–C and C–heteroatom bonds. However, because they contain similar boryl groups, many times their transformation faces the main challenge in controlling the chemo-, regio- and stereoselectivity. One way to overcome these limitations is by installing different boron groups that can provide an opportunity to tune their reactivity toward better chemo-, regio- and stereoselectivity. Yet, the preparation of polyborylated-alkenes containing different boryl groups has been rare. Herein we report concise, highly site-selective, and stereoselective boron-masking strategies of polyborylated alkenes. This is achieved by designed stereoselective trifluorination and MIDA-ation reactions of readily available starting polyborylated alkenes. Additionally, the trifluoroborylated-alkenes undergo a stereospecific interconversion to Bdan-alkenes. These transition-metal free reactions provide a general and efficient method for the conversion of polyborylated alkenes to access 1,1-di-, 1,2-di-, 1,1,2-tris-(borylated) alkenes containing BF3M, Bdan, and BMIDA, a family of compounds that currently lack efficient synthetic access. Moreover, tetraborylethene undergoes the metal-free MIDA-ation reaction to provide the mono BMIDA tetraboryl alkene selectively. The mixed polyborylalkenes are then demonstrated to be useful in selective C–C and C–heteroatom bond-forming reactions. Given its simplicity and versatility, these stereoselective boron-masking approaches hold great promise for organoboron synthesis and will result in more transformations.https://doi.org/10.1038/s41467-023-37733-0 |
| spellingShingle | Nadim Eghbarieh Nicole Hanania Ahmad Masarwa Stereodefined polymetalloid alkenes synthesis via stereoselective boron-masking of polyborylated alkenes Nature Communications |
| title | Stereodefined polymetalloid alkenes synthesis via stereoselective boron-masking of polyborylated alkenes |
| title_full | Stereodefined polymetalloid alkenes synthesis via stereoselective boron-masking of polyborylated alkenes |
| title_fullStr | Stereodefined polymetalloid alkenes synthesis via stereoselective boron-masking of polyborylated alkenes |
| title_full_unstemmed | Stereodefined polymetalloid alkenes synthesis via stereoselective boron-masking of polyborylated alkenes |
| title_short | Stereodefined polymetalloid alkenes synthesis via stereoselective boron-masking of polyborylated alkenes |
| title_sort | stereodefined polymetalloid alkenes synthesis via stereoselective boron masking of polyborylated alkenes |
| url | https://doi.org/10.1038/s41467-023-37733-0 |
| work_keys_str_mv | AT nadimeghbarieh stereodefinedpolymetalloidalkenessynthesisviastereoselectiveboronmaskingofpolyborylatedalkenes AT nicolehanania stereodefinedpolymetalloidalkenessynthesisviastereoselectiveboronmaskingofpolyborylatedalkenes AT ahmadmasarwa stereodefinedpolymetalloidalkenessynthesisviastereoselectiveboronmaskingofpolyborylatedalkenes |