Direct and enantioselective {alpha}-allylation of ketones via singly occupied molecular orbital (SOMO) catalysis
The first enantioselective organocatalytic α-allylation of cyclic ketones has been accomplished via singly occupied molecular orbital catalysis. Geometrically constrained radical cations, forged from the one-electron oxidation of transiently generated enamines, readily undergo allylic alkylation wit...
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| Veröffentlicht in: | Proceedings of the National Academy of Sciences - PNAS 2010-11, Vol.107 (48), p.20648-20651 |
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| container_issue | 48 |
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| container_title | Proceedings of the National Academy of Sciences - PNAS |
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| creator | Mastracchio, Anthony Warkentin, Alexander A Walji, Abbas M MacMillan, David W C |
| description | The first enantioselective organocatalytic α-allylation of cyclic ketones has been accomplished via singly occupied molecular orbital catalysis. Geometrically constrained radical cations, forged from the one-electron oxidation of transiently generated enamines, readily undergo allylic alkylation with a variety of commercially available allyl silanes. A reasonable latitude in both the ketone and allyl silane components is readily accommodated in this new transformation. Moreover, three new oxidatively stable imidazolidinone catalysts have been developed that allow cyclic ketones to successfully participate in this transformation. The new catalyst platform has also been exploited in the first catalytic enantioselective α-enolation and α-carbooxidation of ketones. |
| doi_str_mv | 10.1073/pnas.1002845107 |
| format | Article |
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| ispartof | Proceedings of the National Academy of Sciences - PNAS, 2010-11, Vol.107 (48), p.20648-20651 |
| issn | 0027-8424 1091-6490 |
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| source | Jstor Complete Legacy; PubMed Central; Alma/SFX Local Collection; Free Full-Text Journals in Chemistry |
| subjects | Catalysis Catalysts Chemical reactions Molecular chemistry Organic chemicals Oxidation |
| title | Direct and enantioselective {alpha}-allylation of ketones via singly occupied molecular orbital (SOMO) catalysis |
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