Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes
Gold-catalyzed intermolecular oxidation of carboxylates of primary or secondary propargylic alcohols are realized with excellent regioselectivity, which is ascribed to inductive polarization of the C–C triple bond by the electron-withdrawing carboxy group. The gold carbene intermediates thus generat...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2013-09-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.9.227 |
| _version_ | 1818615959799201792 |
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| author | Kegong Ji Jonathan Nelson Liming Zhang |
| author_facet | Kegong Ji Jonathan Nelson Liming Zhang |
| author_sort | Kegong Ji |
| collection | DOAJ |
| description | Gold-catalyzed intermolecular oxidation of carboxylates of primary or secondary propargylic alcohols are realized with excellent regioselectivity, which is ascribed to inductive polarization of the C–C triple bond by the electron-withdrawing carboxy group. The gold carbene intermediates thus generated undergo selective 1,2-acyloxy migration over a 1,2-C–H insertion, and the selectivities could be dramatically improved by the use of a P,S-bidentate ligand, which is proposed to enable the formation of tris-coordinated and hence less electrophilic gold carbene species. α-Carboxy α,β-unsaturated ketones/aldehydes can be obtained with fair to excellent yields. |
| first_indexed | 2024-12-16T16:42:12Z |
| format | Article |
| id | doaj.art-feb944f614ae42acb7b471afa33fa8b9 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-16T16:42:12Z |
| publishDate | 2013-09-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-feb944f614ae42acb7b471afa33fa8b92022-12-21T22:24:16ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972013-09-01911925193010.3762/bjoc.9.2271860-5397-9-227Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydesKegong Ji0Jonathan Nelson1Liming Zhang2Department of Chemistry and Biochemistry, University of California, Santa Barbara, California, 93106, USADepartment of Chemistry and Biochemistry, University of California, Santa Barbara, California, 93106, USADepartment of Chemistry and Biochemistry, University of California, Santa Barbara, California, 93106, USAGold-catalyzed intermolecular oxidation of carboxylates of primary or secondary propargylic alcohols are realized with excellent regioselectivity, which is ascribed to inductive polarization of the C–C triple bond by the electron-withdrawing carboxy group. The gold carbene intermediates thus generated undergo selective 1,2-acyloxy migration over a 1,2-C–H insertion, and the selectivities could be dramatically improved by the use of a P,S-bidentate ligand, which is proposed to enable the formation of tris-coordinated and hence less electrophilic gold carbene species. α-Carboxy α,β-unsaturated ketones/aldehydes can be obtained with fair to excellent yields.https://doi.org/10.3762/bjoc.9.227enonegold catalysisoxidationpropargyl carboxylate |
| spellingShingle | Kegong Ji Jonathan Nelson Liming Zhang Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes Beilstein Journal of Organic Chemistry enone gold catalysis oxidation propargyl carboxylate |
| title | Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes |
| title_full | Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes |
| title_fullStr | Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes |
| title_full_unstemmed | Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes |
| title_short | Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes |
| title_sort | gold catalyzed regioselective oxidation of propargylic carboxylates a reliable access to α carboxy α β unsaturated ketones aldehydes |
| topic | enone gold catalysis oxidation propargyl carboxylate |
| url | https://doi.org/10.3762/bjoc.9.227 |
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