Site-selective C–H benzylation of alkanes with N-triftosylhydrazones leading to alkyl aromatics
Alkanes are an abundant and valuable resource for transformation into value-added fine chemicals. However, selective functionalization of specific C(sp3)–H bonds in alkanes for alkyl-alkyl bond formation is a significant challenge because of their intrinsic inertness and the small differences in rea...
| Main Authors: | , , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
Cell Press
2020
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| _version_ | 1797059166097899520 |
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| author | Liu, Z Cao, S Yu, W Wu, J Yi, F Anderson, EA Bi, X |
| author_facet | Liu, Z Cao, S Yu, W Wu, J Yi, F Anderson, EA Bi, X |
| author_sort | Liu, Z |
| collection | OXFORD |
| description | Alkanes are an abundant and valuable resource for transformation into value-added fine chemicals. However, selective functionalization of specific C(sp3)–H bonds in alkanes for alkyl-alkyl bond formation is a significant challenge because of their intrinsic inertness and the small differences in reactivity among various C(sp3)–H bonds. Here, we report a silver-catalyzed site-selective C(sp3)–H benzylation of simple alkanes using N-triftosylhydrazones as a convenient carbene precursor, which enables the synthesis of high value-added alkylated aromatics. A one-pot two-step protocol starting from aldehydes was also realized, thereby constituting a formal reductive alkylation of aryl aldehydes by alkanes. Experimental investigations and DFT calculations reveal that the role of the [TpBr3Ag]2 catalyst is 3-fold: it modulates the carbene reactivity, inhibits carbene dimerization, and avoids over insertion of the product. All three aspects are crucial for the success of this first site-selective intermolecular insertion of donor carbenes into C(sp3)–H bonds of simple alkanes.
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| first_indexed | 2024-03-06T20:00:19Z |
| format | Journal article |
| id | oxford-uuid:2712f1d1-491a-45a7-be25-7c4ed3d87ade |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T20:00:19Z |
| publishDate | 2020 |
| publisher | Cell Press |
| record_format | dspace |
| spelling | oxford-uuid:2712f1d1-491a-45a7-be25-7c4ed3d87ade2022-03-26T12:04:42ZSite-selective C–H benzylation of alkanes with N-triftosylhydrazones leading to alkyl aromaticsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:2712f1d1-491a-45a7-be25-7c4ed3d87adeEnglishSymplectic ElementsCell Press2020Liu, ZCao, SYu, WWu, JYi, FAnderson, EABi, XAlkanes are an abundant and valuable resource for transformation into value-added fine chemicals. However, selective functionalization of specific C(sp3)–H bonds in alkanes for alkyl-alkyl bond formation is a significant challenge because of their intrinsic inertness and the small differences in reactivity among various C(sp3)–H bonds. Here, we report a silver-catalyzed site-selective C(sp3)–H benzylation of simple alkanes using N-triftosylhydrazones as a convenient carbene precursor, which enables the synthesis of high value-added alkylated aromatics. A one-pot two-step protocol starting from aldehydes was also realized, thereby constituting a formal reductive alkylation of aryl aldehydes by alkanes. Experimental investigations and DFT calculations reveal that the role of the [TpBr3Ag]2 catalyst is 3-fold: it modulates the carbene reactivity, inhibits carbene dimerization, and avoids over insertion of the product. All three aspects are crucial for the success of this first site-selective intermolecular insertion of donor carbenes into C(sp3)–H bonds of simple alkanes. |
| spellingShingle | Liu, Z Cao, S Yu, W Wu, J Yi, F Anderson, EA Bi, X Site-selective C–H benzylation of alkanes with N-triftosylhydrazones leading to alkyl aromatics |
| title | Site-selective C–H benzylation of alkanes with N-triftosylhydrazones leading to alkyl aromatics |
| title_full | Site-selective C–H benzylation of alkanes with N-triftosylhydrazones leading to alkyl aromatics |
| title_fullStr | Site-selective C–H benzylation of alkanes with N-triftosylhydrazones leading to alkyl aromatics |
| title_full_unstemmed | Site-selective C–H benzylation of alkanes with N-triftosylhydrazones leading to alkyl aromatics |
| title_short | Site-selective C–H benzylation of alkanes with N-triftosylhydrazones leading to alkyl aromatics |
| title_sort | site selective c h benzylation of alkanes with n triftosylhydrazones leading to alkyl aromatics |
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