Pentafulvene for the Synthesis of Complex Natural Products: Total Syntheses of (±)-Pallambins A and B

The first total syntheses of pallambins A and B are enabled by the use of pentafulvene in an unprecedented Diels–Alder reaction. After elaboration of the adduct through chemoselective cyclopropanation, strategic CH insertion affords the dense tetracyclic core of the natural products. 1,3‐Dipolar cy...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2015-09, Vol.54 (38), p.11227-11230
Main Authors: Ebner, Christian, Carreira, Erick M.
Format: Article
Language:English
Subjects:
Biological Products - chemical synthesis
cycloaddition
Cyclopentanes - chemistry
CH insertion
Diterpenes - chemical synthesis
natural products
small-ring systems
total synthesis
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The first total syntheses of pallambins A and B are enabled by the use of pentafulvene in an unprecedented Diels–Alder reaction. After elaboration of the adduct through chemoselective cyclopropanation, strategic CH insertion affords the dense tetracyclic core of the natural products. 1,3‐Dipolar cycloaddition and palladium(II)‐catalyzed alkoxycarbonylation were leveraged for the construction of the hexacyclic scaffold en route to both natural products. Core congestion: The first total syntheses of the diterpenoids (±)‐pallambins A and B are reported. The use of fulvene in a Diels–Alder cycloaddition is without precedence in complex synthesis and enables, in combination with a strategic CH insertion, rapid assembly of the tetracyclo[4.4.03,5.02,8]decane core.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201505126