Iridium-catalyzed reductive allylation of esters
The catalytic reductive transformation of carboxylic esters into α-branched ethers is described. The procedure pivots on the chemoselective iridium-catalyzed hydrosilylation of ester and lactone functionality to afford a silyl acetal intermediate. Upon treatment with a Lewis acid, these hemilabile i...
| Autori principali: | , , , , |
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| Natura: | Journal article |
| Lingua: | English |
| Pubblicazione: |
American Chemical Society
2019
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| _version_ | 1826298536965177344 |
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| author | Xie, L Rogers, J Anastasiou, I Leitch, J Dixon, D |
| author_facet | Xie, L Rogers, J Anastasiou, I Leitch, J Dixon, D |
| author_sort | Xie, L |
| collection | OXFORD |
| description | The catalytic reductive transformation of carboxylic esters into α-branched ethers is described. The procedure pivots on the chemoselective iridium-catalyzed hydrosilylation of ester and lactone functionality to afford a silyl acetal intermediate. Upon treatment with a Lewis acid, these hemilabile intermediates dissociate to form reactive oxocarbenium ions, which can be intercepted by allyltributyltin nucleophiles, resulting in the formation of valuable α-branched alkyl-alkyl ether derivatives. This reductive allylation procedure was found to be amenable to a range of carboxylic ester starting materials, and good chemoselectivity for ethyl over tert-butyl esters was demonstrated. Furthermore, downstream synthetic manipulation of α-amino acid-derived products led to the efficient formation of pyrrolidine, piperidine, and azepane frameworks. |
| first_indexed | 2024-03-07T04:48:22Z |
| format | Journal article |
| id | oxford-uuid:d416651e-2f0e-461e-aab4-a8f5cbc24aa9 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T04:48:22Z |
| publishDate | 2019 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:d416651e-2f0e-461e-aab4-a8f5cbc24aa92022-03-27T08:15:58ZIridium-catalyzed reductive allylation of estersJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:d416651e-2f0e-461e-aab4-a8f5cbc24aa9EnglishSymplectic Elements at OxfordAmerican Chemical Society2019Xie, LRogers, JAnastasiou, ILeitch, JDixon, DThe catalytic reductive transformation of carboxylic esters into α-branched ethers is described. The procedure pivots on the chemoselective iridium-catalyzed hydrosilylation of ester and lactone functionality to afford a silyl acetal intermediate. Upon treatment with a Lewis acid, these hemilabile intermediates dissociate to form reactive oxocarbenium ions, which can be intercepted by allyltributyltin nucleophiles, resulting in the formation of valuable α-branched alkyl-alkyl ether derivatives. This reductive allylation procedure was found to be amenable to a range of carboxylic ester starting materials, and good chemoselectivity for ethyl over tert-butyl esters was demonstrated. Furthermore, downstream synthetic manipulation of α-amino acid-derived products led to the efficient formation of pyrrolidine, piperidine, and azepane frameworks. |
| spellingShingle | Xie, L Rogers, J Anastasiou, I Leitch, J Dixon, D Iridium-catalyzed reductive allylation of esters |
| title | Iridium-catalyzed reductive allylation of esters |
| title_full | Iridium-catalyzed reductive allylation of esters |
| title_fullStr | Iridium-catalyzed reductive allylation of esters |
| title_full_unstemmed | Iridium-catalyzed reductive allylation of esters |
| title_short | Iridium-catalyzed reductive allylation of esters |
| title_sort | iridium catalyzed reductive allylation of esters |
| work_keys_str_mv | AT xiel iridiumcatalyzedreductiveallylationofesters AT rogersj iridiumcatalyzedreductiveallylationofesters AT anastasioui iridiumcatalyzedreductiveallylationofesters AT leitchj iridiumcatalyzedreductiveallylationofesters AT dixond iridiumcatalyzedreductiveallylationofesters |