Reversible [4 + 1] Cycloaddition of Arenes by a “Naked” Acyclic Aluminyl Compound
The large steric profile of the N-heterocyclic boryloxy ligand, –OB(NDippCH)2, and its ability to stabilize the metal-centered HOMO, are exploited in the synthesis of the first example of a “naked” acyclic aluminyl complex, [K(2.2.2-crypt)][Al{OB(NDippCH)2}2]. This system, which is formed by su...
| Main Authors: | , , , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
American Chemical Society
2024
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| _version_ | 1826313569314013184 |
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| author | Sarkar, D Vasko, P Roper, AF Crumpton, AE Roy, MMD Griffin, LP Bogle, C Aldridge, S |
| author_facet | Sarkar, D Vasko, P Roper, AF Crumpton, AE Roy, MMD Griffin, LP Bogle, C Aldridge, S |
| author_sort | Sarkar, D |
| collection | OXFORD |
| description | The large steric profile of the N-heterocyclic boryloxy ligand, –OB(NDippCH)2, and its ability to stabilize the metal-centered HOMO, are exploited in the synthesis of the first example of a “naked” acyclic aluminyl complex, [K(2.2.2-crypt)][Al{OB(NDippCH)2}2]. This system, which is formed by substitution at AlI (rather than reduction of AlIII), represents the first O-ligated aluminyl compound and is shown to be capable of hitherto unprecedented reversible single-site [4 + 1] cycloaddition of benzene. This chemistry and the unusual regioselectivity of the related cycloaddition of anthracene are shown to be highly dependent on the availability (or otherwise) of the K+ countercation. |
| first_indexed | 2024-09-25T04:15:24Z |
| format | Journal article |
| id | oxford-uuid:5f38a500-50f1-40ce-8a5c-94ae5bb6a84b |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-09-25T04:15:24Z |
| publishDate | 2024 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:5f38a500-50f1-40ce-8a5c-94ae5bb6a84b2024-07-20T14:41:42ZReversible [4 + 1] Cycloaddition of Arenes by a “Naked” Acyclic Aluminyl CompoundJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:5f38a500-50f1-40ce-8a5c-94ae5bb6a84bEnglishJisc Publications RouterAmerican Chemical Society2024Sarkar, DVasko, PRoper, AFCrumpton, AERoy, MMDGriffin, LPBogle, CAldridge, SThe large steric profile of the N-heterocyclic boryloxy ligand, –OB(NDippCH)2, and its ability to stabilize the metal-centered HOMO, are exploited in the synthesis of the first example of a “naked” acyclic aluminyl complex, [K(2.2.2-crypt)][Al{OB(NDippCH)2}2]. This system, which is formed by substitution at AlI (rather than reduction of AlIII), represents the first O-ligated aluminyl compound and is shown to be capable of hitherto unprecedented reversible single-site [4 + 1] cycloaddition of benzene. This chemistry and the unusual regioselectivity of the related cycloaddition of anthracene are shown to be highly dependent on the availability (or otherwise) of the K+ countercation. |
| spellingShingle | Sarkar, D Vasko, P Roper, AF Crumpton, AE Roy, MMD Griffin, LP Bogle, C Aldridge, S Reversible [4 + 1] Cycloaddition of Arenes by a “Naked” Acyclic Aluminyl Compound |
| title | Reversible [4 + 1] Cycloaddition of Arenes by a “Naked” Acyclic Aluminyl Compound |
| title_full | Reversible [4 + 1] Cycloaddition of Arenes by a “Naked” Acyclic Aluminyl Compound |
| title_fullStr | Reversible [4 + 1] Cycloaddition of Arenes by a “Naked” Acyclic Aluminyl Compound |
| title_full_unstemmed | Reversible [4 + 1] Cycloaddition of Arenes by a “Naked” Acyclic Aluminyl Compound |
| title_short | Reversible [4 + 1] Cycloaddition of Arenes by a “Naked” Acyclic Aluminyl Compound |
| title_sort | reversible 4 1 cycloaddition of arenes by a naked acyclic aluminyl compound |
| work_keys_str_mv | AT sarkard reversible41cycloadditionofarenesbyanakedacyclicaluminylcompound AT vaskop reversible41cycloadditionofarenesbyanakedacyclicaluminylcompound AT roperaf reversible41cycloadditionofarenesbyanakedacyclicaluminylcompound AT crumptonae reversible41cycloadditionofarenesbyanakedacyclicaluminylcompound AT roymmd reversible41cycloadditionofarenesbyanakedacyclicaluminylcompound AT griffinlp reversible41cycloadditionofarenesbyanakedacyclicaluminylcompound AT boglec reversible41cycloadditionofarenesbyanakedacyclicaluminylcompound AT aldridges reversible41cycloadditionofarenesbyanakedacyclicaluminylcompound |