Stereoselective Total Synthesis of the Dimeric Naphthoquinonopyrano-γ-lactone (-)-Crisamicin A : Introducing the Dimerization Site by a Late-Stage Hartwig Borylation
The first stereoselective total synthesis of the dimeric naphthoquinonopyrano-γ-lactone (-)-crisamicin A was realized (13 steps, 5% overall yield). 1,4,5-Trimethoxynaphthalene, reached in five known steps, was brominated at C-3 to install a but-3-enoic ester by an ensuing Heck coupling. An asymmetric Sharpless dihydroxylation followed and gave a β-hydroxy-γ-lactone with >99.9% ee. Its OH substituent and acetaldehyde established the dihydropyran ring in a completely diastereoselective oxa-Pictet-Spengler cyclization. The 2,3-fused anisole moiety allowed the C5-H bond under Hartwig's conditions to be borylated. This set the stage for engaging the resulting C5-B bond in an oxidative dimerization, which led to a binaphthohydroquinon-5-yl. The latter was advanced to synthetic crisamicin A by a double CAN oxidation (→ a binaphthoquinon-5-yl) and a double demethylation.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2020 |
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| Erschienen: |
2020 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:22 |
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| Enthalten in: |
Organic letters - 22(2020), 9 vom: 01. Mai, Seite 3607-3612 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Kopp, Julia [VerfasserIn] |
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| Anmerkungen: |
Date Completed 21.09.2020 Date Revised 21.09.2020 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.orglett.0c01078 |
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| funding: |
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NLM308830040 |
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| 245 | 1 | 0 | |a Stereoselective Total Synthesis of the Dimeric Naphthoquinonopyrano-γ-lactone (-)-Crisamicin A |b Introducing the Dimerization Site by a Late-Stage Hartwig Borylation |
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| 500 | |a Date Revised 21.09.2020 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a The first stereoselective total synthesis of the dimeric naphthoquinonopyrano-γ-lactone (-)-crisamicin A was realized (13 steps, 5% overall yield). 1,4,5-Trimethoxynaphthalene, reached in five known steps, was brominated at C-3 to install a but-3-enoic ester by an ensuing Heck coupling. An asymmetric Sharpless dihydroxylation followed and gave a β-hydroxy-γ-lactone with >99.9% ee. Its OH substituent and acetaldehyde established the dihydropyran ring in a completely diastereoselective oxa-Pictet-Spengler cyclization. The 2,3-fused anisole moiety allowed the C5-H bond under Hartwig's conditions to be borylated. This set the stage for engaging the resulting C5-B bond in an oxidative dimerization, which led to a binaphthohydroquinon-5-yl. The latter was advanced to synthetic crisamicin A by a double CAN oxidation (→ a binaphthoquinon-5-yl) and a double demethylation | ||
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