Total Synthesis of Anti‐Cancer Meroterpenoids Dysideanone B and Dysiherbol A and Structural Reassignment of Dysiherbol A
The first total synthesis of marine anti‐cancer meroterpenoids dysideanone B and dysiherbol A have been accomplished in a divergent way. The synthetic route features: 1) a site and stereoselective α‐position alkylation of a Wieland–Miescher ketone derivative with a bulky benzyl bromide to join the t...
Saved in:
Published in | Angewandte Chemie Vol. 133; no. 25; pp. 13926 - 13932 |
---|---|
Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
Published |
Weinheim
Wiley Subscription Services, Inc
14.06.2021
|
Subjects | |
Online Access | Get full text |
Cover
Loading…
Summary: | The first total synthesis of marine anti‐cancer meroterpenoids dysideanone B and dysiherbol A have been accomplished in a divergent way. The synthetic route features: 1) a site and stereoselective α‐position alkylation of a Wieland–Miescher ketone derivative with a bulky benzyl bromide to join the terpene and aromatic moieties together and set the stage for subsequent cyclization reactions; 2) an intramolecular radical cyclization to construct the 6/6/6/6‐tetracycle of dysideanone B and an intramolecular Heck reaction to forge the 6/6/5/6‐fused core structure of dysiherbol A. A late‐stage introduction of the ethoxy group in dysideanone B reveals that this group might come from the solvent ethanol. The structure of dysiherbol A has been revised based on our chemical total synthesis.
The first total synthesis of marine anti‐cancer natural products dysideanone B and dysiherbol A have been completed and the structure of dysiherbol A has been revised. A radical cyclization was employed to construct the 6/6/6/6 skeleton of dysideanone B and a Heck reaction was utilized to forge the 6/6/5/6 core structure of dysiherbol A. |
---|---|
Bibliography: | birthday th Dedicated to Professor K. C. Nicolaou on the occasion of his 75 |
ISSN: | 0044-8249 1521-3757 |
DOI: | 10.1002/ange.202100541 |