Ruthenium-catalyzed hydrohydroxyalkylation of acrylates with diols and α-hydroxycarbonyl compounds to form spiro- and α-methylene-γ-butyrolactones
Under the conditions of ruthenium(0)-catalyzed hydrohydroxyalkylation, vicinal diols 1a-1l and methyl acrylate 2a are converted to the corresponding lactones 3a-3l in good to excellent yield. The reactions of methyl acrylate 2a with hydrobenzoin 1f, benzoin didehydro-1f, and benzil tetradehydro-1f form the same lactone 3f product, demonstrating that this process may be deployed in a redox level-independent manner. A variety of substituted acrylic esters 2a-2h participate in spirolactone formation, as illustrated in the conversion of N-benzyl-3-hydroxyoxindole 1o to cycloadducts 4a-4h. Hydrohydroxyalkylation of hydroxyl-substituted methacrylate 2i with diols 1b, 1f, 1j, and 1l forms α-exo-methylene-γ-butyrolactones 5b, 5f, 5j, and 5l in moderate to good yield. A catalytic cycle involving 1,2-dicarbonyl-acrylate oxidative coupling to form oxaruthenacyclic intermediates is postulated. A catalytically competent mononuclear ruthenium(II) complex was characterized by single-crystal X-ray diffraction. The influence of electronic effects on regioselectivity in reactions of nonsymmetric diols was probed using para-substituted 1-phenyl-1,2-propanediols 1g, 1m, and 1n and density functional theory calculations.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2013 |
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| Erschienen: |
2013 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:135 |
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| Enthalten in: |
Journal of the American Chemical Society - 135(2013), 45 vom: 13. Nov., Seite 17230-5 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
McInturff, Emma L [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Completed 17.06.2014 Date Revised 21.10.2021 published: Print-Electronic Citation Status MEDLINE |
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| doi: |
10.1021/ja410533y |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM23226337X |
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| 100 | 1 | |a McInturff, Emma L |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Ruthenium-catalyzed hydrohydroxyalkylation of acrylates with diols and α-hydroxycarbonyl compounds to form spiro- and α-methylene-γ-butyrolactones |
| 264 | 1 | |c 2013 | |
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| 500 | |a Date Completed 17.06.2014 | ||
| 500 | |a Date Revised 21.10.2021 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a Under the conditions of ruthenium(0)-catalyzed hydrohydroxyalkylation, vicinal diols 1a-1l and methyl acrylate 2a are converted to the corresponding lactones 3a-3l in good to excellent yield. The reactions of methyl acrylate 2a with hydrobenzoin 1f, benzoin didehydro-1f, and benzil tetradehydro-1f form the same lactone 3f product, demonstrating that this process may be deployed in a redox level-independent manner. A variety of substituted acrylic esters 2a-2h participate in spirolactone formation, as illustrated in the conversion of N-benzyl-3-hydroxyoxindole 1o to cycloadducts 4a-4h. Hydrohydroxyalkylation of hydroxyl-substituted methacrylate 2i with diols 1b, 1f, 1j, and 1l forms α-exo-methylene-γ-butyrolactones 5b, 5f, 5j, and 5l in moderate to good yield. A catalytic cycle involving 1,2-dicarbonyl-acrylate oxidative coupling to form oxaruthenacyclic intermediates is postulated. A catalytically competent mononuclear ruthenium(II) complex was characterized by single-crystal X-ray diffraction. The influence of electronic effects on regioselectivity in reactions of nonsymmetric diols was probed using para-substituted 1-phenyl-1,2-propanediols 1g, 1m, and 1n and density functional theory calculations | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, N.I.H., Extramural | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 7 | |a Acrylates |2 NLM | |
| 650 | 7 | |a Spiro Compounds |2 NLM | |
| 650 | 7 | |a alpha-methylene gamma-butyrolactone |2 NLM | |
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| 650 | 7 | |a Ruthenium |2 NLM | |
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| 650 | 7 | |a 4-Butyrolactone |2 NLM | |
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| 650 | 7 | |a methyl acrylate |2 NLM | |
| 650 | 7 | |a WC487PR91H |2 NLM | |
| 700 | 1 | |a Mowat, Jeffrey |e verfasserin |4 aut | |
| 700 | 1 | |a Waldeck, Andrew R |e verfasserin |4 aut | |
| 700 | 1 | |a Krische, Michael J |e verfasserin |4 aut | |
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| 856 | 4 | 0 | |u http://dx.doi.org/10.1021/ja410533y |3 Volltext |
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