Expedient Route to the Tigliane-Daphnane Skeleton via Oxonium Ylide [1,2]-Shift

A short, stereoselective approach to the fused tricyclic carbon skeleton found in the tigliane and daphnane classes of diterpene natural products is described. Convergent coupling of the A- and C-rings, followed by diastereoselective cerium enolate addition and formation of a double acetal set the s...

Full description

Saved in:

Bibliographic Details
Published in:	Organic letters Vol. 13; no. 4; pp. 720 - 723
Main Authors:	Stewart, Craig, McDonald, Robert, West, F. G
Format:	Journal Article
Language:	English
Published:	United States American Chemical Society 18-02-2011
Subjects:	Biological Products - chemical synthesis Biological Products - chemistry Diterpenes - chemical synthesis Diterpenes - chemistry Molecular Structure Stereoisomerism
Online Access:	Get full text
Tags:	Add Tag No Tags, Be the first to tag this record!

Description
Summary:	A short, stereoselective approach to the fused tricyclic carbon skeleton found in the tigliane and daphnane classes of diterpene natural products is described. Convergent coupling of the A- and C-rings, followed by diastereoselective cerium enolate addition and formation of a double acetal set the stage for generation of an oxonium ylide via a transient metallocarbene. An efficient Stevens [1,2]-shift furnished the 7-membered B-ring, possessing the bridgehead oxygenation pattern found in the natural systems.
Bibliography:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	1523-7060 1523-7052
DOI:	10.1021/ol102953s