Site- and enantioselective B−H functionalization of carboranes
Abstract Functionalization of carboranes, icosahedral boron−carbon molecular clusters, is of great interest as they have wide applications in medicinal and materials chemistry. Thus, site- and enantioselective synthesis of carboranes requires complete control of the reaction. Herein, we describe the...
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Nature Portfolio
2025-05-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-59410-0 |
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| author | Kyungsup Lee Gisela A. González-Montiel Hyeonsik Eom Tae Hyeon Kim Hee Chan Noh Abdikani Omar Farah Henry R. Wise Dongwook Kim Paul Ha-Yeon Cheong Phil Ho Lee |
| author_facet | Kyungsup Lee Gisela A. González-Montiel Hyeonsik Eom Tae Hyeon Kim Hee Chan Noh Abdikani Omar Farah Henry R. Wise Dongwook Kim Paul Ha-Yeon Cheong Phil Ho Lee |
| author_sort | Kyungsup Lee |
| collection | DOAJ |
| description | Abstract Functionalization of carboranes, icosahedral boron−carbon molecular clusters, is of great interest as they have wide applications in medicinal and materials chemistry. Thus, site- and enantioselective synthesis of carboranes requires complete control of the reaction. Herein, we describe the asymmetric Rh(II)-catalyzed insertion reactions of carbenes into cage B–H bond of carboranes. This reaction thereby generates carboranes possessing a carbon-stereocenter adjacent to cage boron of the carborane, in excellent site- and enantioselectivity under mild reaction conditions. The fully computed transition structures of Rh(II)-catalyzed carbene insertion process through density functional theory are reported. These B–H insertion transition structures, in conjunction with topographical proximity surfaces analyses, visually reveal the region between the carborane and the phthalimide ligands responsible for the selectivities of this reaction. |
| format | Article |
| id | doaj-art-b8cfaf6beb5f4ff09378bdca28de9612 |
| institution | OA Journals |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-05-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-b8cfaf6beb5f4ff09378bdca28de96122025-08-20T02:15:15ZengNature PortfolioNature Communications2041-17232025-05-011611910.1038/s41467-025-59410-0Site- and enantioselective B−H functionalization of carboranesKyungsup Lee0Gisela A. González-Montiel1Hyeonsik Eom2Tae Hyeon Kim3Hee Chan Noh4Abdikani Omar Farah5Henry R. Wise6Dongwook Kim7Paul Ha-Yeon Cheong8Phil Ho Lee9Department of Chemistry, Kangwon National UniversityDepartment of Chemistry, Oregon State University, 153 Gilbert HallDepartment of Chemistry, Kangwon National UniversityDepartment of Chemistry, Kangwon National UniversityDepartment of Chemistry, Kangwon National UniversityDepartment of Chemistry, Oregon State University, 153 Gilbert HallDepartment of Chemistry, Oregon State University, 153 Gilbert HallDepartment of Chemistry, Korea Advanced Institute of Science and TechnologyDepartment of Chemistry, Oregon State University, 153 Gilbert HallDepartment of Chemistry, Kangwon National UniversityAbstract Functionalization of carboranes, icosahedral boron−carbon molecular clusters, is of great interest as they have wide applications in medicinal and materials chemistry. Thus, site- and enantioselective synthesis of carboranes requires complete control of the reaction. Herein, we describe the asymmetric Rh(II)-catalyzed insertion reactions of carbenes into cage B–H bond of carboranes. This reaction thereby generates carboranes possessing a carbon-stereocenter adjacent to cage boron of the carborane, in excellent site- and enantioselectivity under mild reaction conditions. The fully computed transition structures of Rh(II)-catalyzed carbene insertion process through density functional theory are reported. These B–H insertion transition structures, in conjunction with topographical proximity surfaces analyses, visually reveal the region between the carborane and the phthalimide ligands responsible for the selectivities of this reaction.https://doi.org/10.1038/s41467-025-59410-0 |
| spellingShingle | Kyungsup Lee Gisela A. González-Montiel Hyeonsik Eom Tae Hyeon Kim Hee Chan Noh Abdikani Omar Farah Henry R. Wise Dongwook Kim Paul Ha-Yeon Cheong Phil Ho Lee Site- and enantioselective B−H functionalization of carboranes Nature Communications |
| title | Site- and enantioselective B−H functionalization of carboranes |
| title_full | Site- and enantioselective B−H functionalization of carboranes |
| title_fullStr | Site- and enantioselective B−H functionalization of carboranes |
| title_full_unstemmed | Site- and enantioselective B−H functionalization of carboranes |
| title_short | Site- and enantioselective B−H functionalization of carboranes |
| title_sort | site and enantioselective b h functionalization of carboranes |
| url | https://doi.org/10.1038/s41467-025-59410-0 |
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