Formal total synthesis of (-)-apicularen A via transannular conjugate addition

Ferdows Hilli; Jonathan M White; Mark A Rizzacasa

doi:10.1021/ol0497943

Formal total synthesis of (-)-apicularen A via transannular conjugate addition

Org Lett. 2004 Apr 15;6(8):1289-92. doi: 10.1021/ol0497943.

Authors

Ferdows Hilli¹, Jonathan M White, Mark A Rizzacasa

Affiliation

¹ School of Chemistry, The University of Melbourne, Victoria 3010, Australia.

PMID: 15070319
DOI: 10.1021/ol0497943

Abstract

The formal total synthesis of the myxobacteria metabolite (-)-apicularen A (1) is described. The key step involved a novel acid-mediated transannular conjugate addition of the C13 hydroxyl into the alpha,beta-unsaturated ketone in either of the macrolactones 5a or 5b to provide the same trans-pyranone 4. Conversion of 4 into the known apicularen intermediate diol 3 completed the formal synthesis. [reaction: see text]

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Antineoplastic Agents / chemical synthesis*
Antineoplastic Agents / pharmacology
Bridged Bicyclo Compounds, Heterocyclic / chemical synthesis*
Bridged Bicyclo Compounds, Heterocyclic / pharmacology
Catalysis
Cyclization
Ketones / chemistry*
Lactones / chemistry
Macrolides / chemistry
Models, Molecular
Myxococcales / metabolism
Pyrans / chemistry
Stereoisomerism
Temperature

Substances

Antineoplastic Agents
Bridged Bicyclo Compounds, Heterocyclic
Ketones
Lactones
Macrolides
Pyrans
apicularen A