Photocatalyzed regioselective hydrosilylation for the divergent synthesis of geminal and vicinal borosilanes
Abstract Geminal and vicinal borosilanes are useful building blocks in synthetic chemistry and material science. Hydrosilylation/hydroborylation of unsaturated systems offer expedient access to these motifs. In contrast to the well-established transition-metal-catalyzed methods, radical approaches a...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-05-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-38224-y |
| _version_ | 1797832041382805504 |
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| author | Degong Kong Muliang Zhang Yuchao Zhang Zhenyang Yu Hui Cao Jie Wu |
| author_facet | Degong Kong Muliang Zhang Yuchao Zhang Zhenyang Yu Hui Cao Jie Wu |
| author_sort | Degong Kong |
| collection | DOAJ |
| description | Abstract Geminal and vicinal borosilanes are useful building blocks in synthetic chemistry and material science. Hydrosilylation/hydroborylation of unsaturated systems offer expedient access to these motifs. In contrast to the well-established transition-metal-catalyzed methods, radical approaches are rarely explored. Herein we report the synthesis of geminal borosilanes from α-selective hydrosilylation of alkenyl boronates via photoinduced hydrogen atom transfer (HAT) catalysis. Mechanistic studies implicate that the α-selectivity originates from a kinetically favored radical addition and an energetically favored HAT process. We further demonstrate selective synthesis of vicinal borosilanes through hydrosilylation of allyl boronates via 1,2-boron radical migration. These strategies exhibit broad scopes across primary, secondary, and tertiary silanes and various boron compounds. The synthetic utility is evidenced by access to multi-borosilanes in a diverse fashion and scaling up by continuous-flow synthesis. |
| first_indexed | 2024-04-09T14:01:22Z |
| format | Article |
| id | doaj.art-a97e40481c214d818d33bb95c58cc2e9 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-04-09T14:01:22Z |
| publishDate | 2023-05-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-a97e40481c214d818d33bb95c58cc2e92023-05-07T11:16:52ZengNature PortfolioNature Communications2041-17232023-05-0114111010.1038/s41467-023-38224-yPhotocatalyzed regioselective hydrosilylation for the divergent synthesis of geminal and vicinal borosilanesDegong Kong0Muliang Zhang1Yuchao Zhang2Zhenyang Yu3Hui Cao4Jie Wu5Department of Chemistry, National University of SingaporeDepartment of Chemistry, National University of SingaporeInstitute of Basic Medicine and Cancer (IBMC), Cancer Hospital of the University of Chinese Academy of SciencesDepartment of Chemistry, National University of SingaporeDepartment of Chemistry, National University of SingaporeDepartment of Chemistry, National University of SingaporeAbstract Geminal and vicinal borosilanes are useful building blocks in synthetic chemistry and material science. Hydrosilylation/hydroborylation of unsaturated systems offer expedient access to these motifs. In contrast to the well-established transition-metal-catalyzed methods, radical approaches are rarely explored. Herein we report the synthesis of geminal borosilanes from α-selective hydrosilylation of alkenyl boronates via photoinduced hydrogen atom transfer (HAT) catalysis. Mechanistic studies implicate that the α-selectivity originates from a kinetically favored radical addition and an energetically favored HAT process. We further demonstrate selective synthesis of vicinal borosilanes through hydrosilylation of allyl boronates via 1,2-boron radical migration. These strategies exhibit broad scopes across primary, secondary, and tertiary silanes and various boron compounds. The synthetic utility is evidenced by access to multi-borosilanes in a diverse fashion and scaling up by continuous-flow synthesis.https://doi.org/10.1038/s41467-023-38224-y |
| spellingShingle | Degong Kong Muliang Zhang Yuchao Zhang Zhenyang Yu Hui Cao Jie Wu Photocatalyzed regioselective hydrosilylation for the divergent synthesis of geminal and vicinal borosilanes Nature Communications |
| title | Photocatalyzed regioselective hydrosilylation for the divergent synthesis of geminal and vicinal borosilanes |
| title_full | Photocatalyzed regioselective hydrosilylation for the divergent synthesis of geminal and vicinal borosilanes |
| title_fullStr | Photocatalyzed regioselective hydrosilylation for the divergent synthesis of geminal and vicinal borosilanes |
| title_full_unstemmed | Photocatalyzed regioselective hydrosilylation for the divergent synthesis of geminal and vicinal borosilanes |
| title_short | Photocatalyzed regioselective hydrosilylation for the divergent synthesis of geminal and vicinal borosilanes |
| title_sort | photocatalyzed regioselective hydrosilylation for the divergent synthesis of geminal and vicinal borosilanes |
| url | https://doi.org/10.1038/s41467-023-38224-y |
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