Asymmetric Total Synthesis of Hetidine-Type C20-Diterpenoid Alkaloids : (+)-Talassimidine and (+)-Talassamine
Here, we report the first asymmetric total synthesis of (+)-talassimidine and (+)-talassamine, two hetidine-type C20-diterpenoid alkaloids. A highly regio- and diastereoselective 1,3-dipolar cycloaddition of an azomethine ylide yielded a chiral tetracyclic intermediate in high enantiopurity, thus providing the structural basis for asymmetric assembly of the hexacyclic hetidine skeleton. In this key step, the introduction of a single chiral center induces four new continuous chiral centers. Another key transformation is the dearomative cyclopropanation of the benzene ring and subsequent SN2-like ring opening of the resultant cyclopropane ring with water as a nucleophile, which not only establishes the B ring but also precisely installs the difficult-to-achieve equatorial C7-OH group.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2021 |
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| Erschienen: |
2021 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:143 |
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| Enthalten in: |
Journal of the American Chemical Society - 143(2021), 18 vom: 12. Mai, Seite 7088-7095 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Zhang, Quanzheng [VerfasserIn] |
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| Links: |
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| Themen: |
Alkaloids |
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| Anmerkungen: |
Date Completed 03.12.2021 Date Revised 14.12.2021 published: Print-Electronic Citation Status MEDLINE |
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| doi: |
10.1021/jacs.1c01865 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM324913184 |
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| 100 | 1 | |a Zhang, Quanzheng |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Asymmetric Total Synthesis of Hetidine-Type C20-Diterpenoid Alkaloids |b (+)-Talassimidine and (+)-Talassamine |
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| 500 | |a Date Completed 03.12.2021 | ||
| 500 | |a Date Revised 14.12.2021 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a Here, we report the first asymmetric total synthesis of (+)-talassimidine and (+)-talassamine, two hetidine-type C20-diterpenoid alkaloids. A highly regio- and diastereoselective 1,3-dipolar cycloaddition of an azomethine ylide yielded a chiral tetracyclic intermediate in high enantiopurity, thus providing the structural basis for asymmetric assembly of the hexacyclic hetidine skeleton. In this key step, the introduction of a single chiral center induces four new continuous chiral centers. Another key transformation is the dearomative cyclopropanation of the benzene ring and subsequent SN2-like ring opening of the resultant cyclopropane ring with water as a nucleophile, which not only establishes the B ring but also precisely installs the difficult-to-achieve equatorial C7-OH group | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 7 | |a Alkaloids |2 NLM | |
| 650 | 7 | |a Diterpenes |2 NLM | |
| 700 | 1 | |a Yang, Zhao |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Qi |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Shuangwei |e verfasserin |4 aut | |
| 700 | 1 | |a Zhou, Tao |e verfasserin |4 aut | |
| 700 | 1 | |a Zhao, Yankun |e verfasserin |4 aut | |
| 700 | 1 | |a Zhang, Min |e verfasserin |4 aut | |
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