Application of Computational Chemical Shift Prediction Techniques to the Cereoanhydride Structure Problem—Carboxylate Complications
Despite the vast array of techniques available to modern-day chemists, structural misassignments still occur. These misassignments are often only realized upon attempted synthesis, when the spectra of synthesized products do not match previously reported spectra. This was the case with marine natura...
| Main Authors: | , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2017-06-01
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| Series: | Marine Drugs |
| Subjects: | |
| Online Access: | http://www.mdpi.com/1660-3397/15/6/171 |
| _version_ | 1798043711003688960 |
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| author | Carla M. Saunders Dean J. Tantillo |
| author_facet | Carla M. Saunders Dean J. Tantillo |
| author_sort | Carla M. Saunders |
| collection | DOAJ |
| description | Despite the vast array of techniques available to modern-day chemists, structural misassignments still occur. These misassignments are often only realized upon attempted synthesis, when the spectra of synthesized products do not match previously reported spectra. This was the case with marine natural product cereoanhydride. The originally proposed 7-membered ring anhydride (1) was shown to be incorrect, although a likely precursor to the correct structure (2) in both its laboratory synthesis and biosynthesis. Herein, in addition to showing how NMR computations could have been used to arrive at the correct structure, we show that the conversion of 1 to 2 is indeed energetically viable, and we highlight complications in predicting NMR chemical shifts for molecules with acidic protons. |
| first_indexed | 2024-04-11T22:52:54Z |
| format | Article |
| id | doaj.art-b1a63cb7159547a6803053a27f1bad7f |
| institution | Directory Open Access Journal |
| issn | 1660-3397 |
| language | English |
| last_indexed | 2024-04-11T22:52:54Z |
| publishDate | 2017-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Marine Drugs |
| spelling | doaj.art-b1a63cb7159547a6803053a27f1bad7f2022-12-22T03:58:32ZengMDPI AGMarine Drugs1660-33972017-06-0115617110.3390/md15060171md15060171Application of Computational Chemical Shift Prediction Techniques to the Cereoanhydride Structure Problem—Carboxylate ComplicationsCarla M. Saunders0Dean J. Tantillo1Department of Chemistry, University of California—Davis, 1 Shields Avenue, Davis, CA 95616, USADepartment of Chemistry, University of California—Davis, 1 Shields Avenue, Davis, CA 95616, USADespite the vast array of techniques available to modern-day chemists, structural misassignments still occur. These misassignments are often only realized upon attempted synthesis, when the spectra of synthesized products do not match previously reported spectra. This was the case with marine natural product cereoanhydride. The originally proposed 7-membered ring anhydride (1) was shown to be incorrect, although a likely precursor to the correct structure (2) in both its laboratory synthesis and biosynthesis. Herein, in addition to showing how NMR computations could have been used to arrive at the correct structure, we show that the conversion of 1 to 2 is indeed energetically viable, and we highlight complications in predicting NMR chemical shifts for molecules with acidic protons.http://www.mdpi.com/1660-3397/15/6/171computational NMRnatural productschemical shifts |
| spellingShingle | Carla M. Saunders Dean J. Tantillo Application of Computational Chemical Shift Prediction Techniques to the Cereoanhydride Structure Problem—Carboxylate Complications Marine Drugs computational NMR natural products chemical shifts |
| title | Application of Computational Chemical Shift Prediction Techniques to the Cereoanhydride Structure Problem—Carboxylate Complications |
| title_full | Application of Computational Chemical Shift Prediction Techniques to the Cereoanhydride Structure Problem—Carboxylate Complications |
| title_fullStr | Application of Computational Chemical Shift Prediction Techniques to the Cereoanhydride Structure Problem—Carboxylate Complications |
| title_full_unstemmed | Application of Computational Chemical Shift Prediction Techniques to the Cereoanhydride Structure Problem—Carboxylate Complications |
| title_short | Application of Computational Chemical Shift Prediction Techniques to the Cereoanhydride Structure Problem—Carboxylate Complications |
| title_sort | application of computational chemical shift prediction techniques to the cereoanhydride structure problem carboxylate complications |
| topic | computational NMR natural products chemical shifts |
| url | http://www.mdpi.com/1660-3397/15/6/171 |
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