Generation of Mixed Anhydrides via Oxidative Fragmentation of Tertiary Cyclopropanols with Phenyliodine(III) Dicarboxylates
Oxidative fragmentation of tertiary cyclopropanols with phenyliodine(III) dicarboxylates in aprotic solvents (dichloromethane, chloroform, toluene) produces mixed anhydrides. The fragmentation reaction is especially facile with phenyliodine(III) reagents bearing electron-withdrawing carboxylate liga...
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MDPI AG
2020-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/1/140 |
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| author | Dzmitry M. Zubrytski Gábor Zoltán Elek Margus Lopp Dzmitry G. Kananovich |
| author_facet | Dzmitry M. Zubrytski Gábor Zoltán Elek Margus Lopp Dzmitry G. Kananovich |
| author_sort | Dzmitry M. Zubrytski |
| collection | DOAJ |
| description | Oxidative fragmentation of tertiary cyclopropanols with phenyliodine(III) dicarboxylates in aprotic solvents (dichloromethane, chloroform, toluene) produces mixed anhydrides. The fragmentation reaction is especially facile with phenyliodine(III) reagents bearing electron-withdrawing carboxylate ligands (trifluoroacetyl, 2,4,6-trichlorobenzoyl, 3-nitrobenzoyl), and affords 95−98% yields of the corresponding mixed anhydride products. The latter can be straightforwardly applied for the acylation of various nitrogen, oxygen and sulfur-centered nucleophiles (primary and secondary amines, hydroxylamines, primary alcohols, phenols, thiols). Intramolecular acylation yielding macrocyclic lactones can also be performed. The developed transformation has bolstered the synthetic utility of cyclopropanols as pluripotent intermediates in diversity-oriented synthesis of bioactive natural products and their synthetic congeners. For example, it was successfully applied for the last-stage modification of a cyclic peptide to produce a precursor of a known histone deacetylase inhibitor. |
| first_indexed | 2024-03-10T13:39:40Z |
| format | Article |
| id | doaj.art-6926714d5dc24581be8ef8f851a6ca7e |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T13:39:40Z |
| publishDate | 2020-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-6926714d5dc24581be8ef8f851a6ca7e2023-11-21T03:09:53ZengMDPI AGMolecules1420-30492020-12-0126114010.3390/molecules26010140Generation of Mixed Anhydrides via Oxidative Fragmentation of Tertiary Cyclopropanols with Phenyliodine(III) DicarboxylatesDzmitry M. Zubrytski0Gábor Zoltán Elek1Margus Lopp2Dzmitry G. Kananovich3Department of Organic Chemistry, Belarusian State University, Leningradskaya 14, 220050 Minsk, BelarusDepartment of Chemistry and Biotechnology, School of Science, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, EstoniaDepartment of Chemistry and Biotechnology, School of Science, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, EstoniaDepartment of Chemistry and Biotechnology, School of Science, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, EstoniaOxidative fragmentation of tertiary cyclopropanols with phenyliodine(III) dicarboxylates in aprotic solvents (dichloromethane, chloroform, toluene) produces mixed anhydrides. The fragmentation reaction is especially facile with phenyliodine(III) reagents bearing electron-withdrawing carboxylate ligands (trifluoroacetyl, 2,4,6-trichlorobenzoyl, 3-nitrobenzoyl), and affords 95−98% yields of the corresponding mixed anhydride products. The latter can be straightforwardly applied for the acylation of various nitrogen, oxygen and sulfur-centered nucleophiles (primary and secondary amines, hydroxylamines, primary alcohols, phenols, thiols). Intramolecular acylation yielding macrocyclic lactones can also be performed. The developed transformation has bolstered the synthetic utility of cyclopropanols as pluripotent intermediates in diversity-oriented synthesis of bioactive natural products and their synthetic congeners. For example, it was successfully applied for the last-stage modification of a cyclic peptide to produce a precursor of a known histone deacetylase inhibitor.https://www.mdpi.com/1420-3049/26/1/140cyclopropanolsmixed anhydridesamidesmacrolactonizationhypervalent iodine reagentsacylation |
| spellingShingle | Dzmitry M. Zubrytski Gábor Zoltán Elek Margus Lopp Dzmitry G. Kananovich Generation of Mixed Anhydrides via Oxidative Fragmentation of Tertiary Cyclopropanols with Phenyliodine(III) Dicarboxylates Molecules cyclopropanols mixed anhydrides amides macrolactonization hypervalent iodine reagents acylation |
| title | Generation of Mixed Anhydrides via Oxidative Fragmentation of Tertiary Cyclopropanols with Phenyliodine(III) Dicarboxylates |
| title_full | Generation of Mixed Anhydrides via Oxidative Fragmentation of Tertiary Cyclopropanols with Phenyliodine(III) Dicarboxylates |
| title_fullStr | Generation of Mixed Anhydrides via Oxidative Fragmentation of Tertiary Cyclopropanols with Phenyliodine(III) Dicarboxylates |
| title_full_unstemmed | Generation of Mixed Anhydrides via Oxidative Fragmentation of Tertiary Cyclopropanols with Phenyliodine(III) Dicarboxylates |
| title_short | Generation of Mixed Anhydrides via Oxidative Fragmentation of Tertiary Cyclopropanols with Phenyliodine(III) Dicarboxylates |
| title_sort | generation of mixed anhydrides via oxidative fragmentation of tertiary cyclopropanols with phenyliodine iii dicarboxylates |
| topic | cyclopropanols mixed anhydrides amides macrolactonization hypervalent iodine reagents acylation |
| url | https://www.mdpi.com/1420-3049/26/1/140 |
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