General pyrrolidine synthesis via iridium-catalyzed reductive azomethine ylide generation from tertiary amides and lactams
An iridium-catalyzed reductive generation of both stabilized and unstabilized azomethine ylides and their application to functionalized pyrrolidine synthesis via [3 + 2] dipolar cycloaddition reactions is described. Proceeding under mild reaction conditions from both amide and lactam precursors poss...
| Glavni autori: | , , , , , , |
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| Format: | Journal article |
| Jezik: | English |
| Izdano: |
American Chemical Society
2021
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| _version_ | 1826286900525137920 |
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| author | Yamazaki, K Gabriel, P Di Carmine, G Pedroni, J Farizyan, M Hamlin, TA Dixon, DJ |
| author_facet | Yamazaki, K Gabriel, P Di Carmine, G Pedroni, J Farizyan, M Hamlin, TA Dixon, DJ |
| author_sort | Yamazaki, K |
| collection | OXFORD |
| description | An iridium-catalyzed reductive generation of both stabilized and unstabilized azomethine ylides and their application to functionalized pyrrolidine synthesis via [3 + 2] dipolar cycloaddition reactions is described. Proceeding under mild reaction conditions from both amide and lactam precursors possessing a suitably positioned electron-withdrawing or a trimethylsilyl group, using 1 mol% Vaska’s complex [IrCl(CO)(PPh3)2] and tetramethyldisiloxane (TMDS) as a terminal reductant, a broad range of (un)stabilized azomethine ylides were accessible. Subsequent regio- and diastereoselective, inter- and intramolecular dipolar cycloaddition reactions with variously substituted electron-deficient alkenes enabled ready and efficient access to structurally complex pyrrolidine architectures. Density functional theory (DFT) calculations of the dipolar cycloaddition reactions uncovered an intimate balance between asynchronicity and interaction energies of transition structures, which ultimately control the unusual selectivities observed in certain cases. |
| first_indexed | 2024-03-07T01:50:35Z |
| format | Journal article |
| id | oxford-uuid:99f56a40-3da5-4752-958b-4c7b2aa7dfed |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T01:50:35Z |
| publishDate | 2021 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:99f56a40-3da5-4752-958b-4c7b2aa7dfed2022-03-27T00:18:00ZGeneral pyrrolidine synthesis via iridium-catalyzed reductive azomethine ylide generation from tertiary amides and lactamsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:99f56a40-3da5-4752-958b-4c7b2aa7dfedEnglishSymplectic ElementsAmerican Chemical Society2021Yamazaki, KGabriel, PDi Carmine, GPedroni, JFarizyan, MHamlin, TADixon, DJAn iridium-catalyzed reductive generation of both stabilized and unstabilized azomethine ylides and their application to functionalized pyrrolidine synthesis via [3 + 2] dipolar cycloaddition reactions is described. Proceeding under mild reaction conditions from both amide and lactam precursors possessing a suitably positioned electron-withdrawing or a trimethylsilyl group, using 1 mol% Vaska’s complex [IrCl(CO)(PPh3)2] and tetramethyldisiloxane (TMDS) as a terminal reductant, a broad range of (un)stabilized azomethine ylides were accessible. Subsequent regio- and diastereoselective, inter- and intramolecular dipolar cycloaddition reactions with variously substituted electron-deficient alkenes enabled ready and efficient access to structurally complex pyrrolidine architectures. Density functional theory (DFT) calculations of the dipolar cycloaddition reactions uncovered an intimate balance between asynchronicity and interaction energies of transition structures, which ultimately control the unusual selectivities observed in certain cases. |
| spellingShingle | Yamazaki, K Gabriel, P Di Carmine, G Pedroni, J Farizyan, M Hamlin, TA Dixon, DJ General pyrrolidine synthesis via iridium-catalyzed reductive azomethine ylide generation from tertiary amides and lactams |
| title | General pyrrolidine synthesis via iridium-catalyzed reductive azomethine ylide generation from tertiary amides and lactams |
| title_full | General pyrrolidine synthesis via iridium-catalyzed reductive azomethine ylide generation from tertiary amides and lactams |
| title_fullStr | General pyrrolidine synthesis via iridium-catalyzed reductive azomethine ylide generation from tertiary amides and lactams |
| title_full_unstemmed | General pyrrolidine synthesis via iridium-catalyzed reductive azomethine ylide generation from tertiary amides and lactams |
| title_short | General pyrrolidine synthesis via iridium-catalyzed reductive azomethine ylide generation from tertiary amides and lactams |
| title_sort | general pyrrolidine synthesis via iridium catalyzed reductive azomethine ylide generation from tertiary amides and lactams |
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