A New Approach to Models of the 4,5-Dihydroxycyclopentenone Core of the Kodaistatins A-D : Elucidation of the Diol Configuration in Kodaistatin A
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim..
The kodaistatins A-D are strongly anti-diabetic natural products from Aspergillus terreus that hold some promise of a novel diabetes cure. However, considerations of that kind face two drawbacks: 1) The kodaistatins A-D contain a heavily substituted pulvinone/cyclopentenone combination; 2) they are 1,2-diols, the 3D structures of which have not been assigned yet. However, we can exclude two of the four possible stereostructures. We conclude that kodaistatin A is a trans-, not a cis-diol from NMR comparisons with a pair of cis, trans-isomeric kodaistatin models, which we synthesized in 11 and 12 steps, respectively. The stereocenters of the diol moiety arose from stereocomplementary, highly diastereoselective aldol additions of a lithium enolate or the corresponding silyl ketene acetal. The cyclopentenone moieties stemmed from intramolecular aldol additions and ensuing dehydrations. The requisite enolates were obtained by the reduction of α-bromoketones with samarium diiodide.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2017 |
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| Erschienen: |
2017 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:23 |
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| Enthalten in: |
Chemistry (Weinheim an der Bergstrasse, Germany) - 23(2017), 50 vom: 07. Sept., Seite 12104-12109 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Peter, David [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Completed 05.04.2018 Date Revised 30.04.2018 published: Print-Electronic Citation Status MEDLINE |
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| doi: |
10.1002/chem.201701185 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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NLM271084413 |
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| 100 | 1 | |a Peter, David |e verfasserin |4 aut | |
| 245 | 1 | 2 | |a A New Approach to Models of the 4,5-Dihydroxycyclopentenone Core of the Kodaistatins A-D |b Elucidation of the Diol Configuration in Kodaistatin A |
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| 500 | |a Date Completed 05.04.2018 | ||
| 500 | |a Date Revised 30.04.2018 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. | ||
| 520 | |a The kodaistatins A-D are strongly anti-diabetic natural products from Aspergillus terreus that hold some promise of a novel diabetes cure. However, considerations of that kind face two drawbacks: 1) The kodaistatins A-D contain a heavily substituted pulvinone/cyclopentenone combination; 2) they are 1,2-diols, the 3D structures of which have not been assigned yet. However, we can exclude two of the four possible stereostructures. We conclude that kodaistatin A is a trans-, not a cis-diol from NMR comparisons with a pair of cis, trans-isomeric kodaistatin models, which we synthesized in 11 and 12 steps, respectively. The stereocenters of the diol moiety arose from stereocomplementary, highly diastereoselective aldol additions of a lithium enolate or the corresponding silyl ketene acetal. The cyclopentenone moieties stemmed from intramolecular aldol additions and ensuing dehydrations. The requisite enolates were obtained by the reduction of α-bromoketones with samarium diiodide | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a aldol reaction | |
| 650 | 4 | |a cyclopentenone | |
| 650 | 4 | |a samarium enolate | |
| 650 | 4 | |a structure elucidation | |
| 650 | 4 | |a α-bromoketones | |
| 650 | 7 | |a Cyclopentanes |2 NLM | |
| 650 | 7 | |a Lactones |2 NLM | |
| 650 | 7 | |a kodaistatin A |2 NLM | |
| 650 | 7 | |a kodaistatin B |2 NLM | |
| 650 | 7 | |a kodaistatin C |2 NLM | |
| 650 | 7 | |a kodaistatin D |2 NLM | |
| 650 | 7 | |a Lithium |2 NLM | |
| 650 | 7 | |a 9FN79X2M3F |2 NLM | |
| 650 | 7 | |a cyclopentenone |2 NLM | |
| 650 | 7 | |a Q0U2IGF9CK |2 NLM | |
| 700 | 1 | |a Brückner, Reinhard |e verfasserin |4 aut | |
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| 773 | 1 | 8 | |g volume:23 |g year:2017 |g number:50 |g day:07 |g month:09 |g pages:12104-12109 |
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