Synthesis 2001; 112(08): 1185-1196
DOI: 10.1055/s-2001-15066
PAPER
Georg Thieme Verlag KG Stuttgart · New York

Fusicoccin Synthesis by Intramolecular [4+4] Photocycloaddition of 2-Pyridones: Stereocontrol of the Cycloaddition and Elaboration of the Pentacyclic Product[*]

Kevin F. McGee Jr.
1  Department of Chemistry, State University of New York, Stony Brook, New York 11794–3400, USA
,
Taleb H. Al-Tel
1  Department of Chemistry, State University of New York, Stony Brook, New York 11794–3400, USA
,
Scott McN. Sieburth
1  Department of Chemistry, State University of New York, Stony Brook, New York 11794–3400, USA
› Author Affiliations
Further Information

Publication History

received 05 March 2001
revised 29 March 2001

Publication Date:
24 September 2004 (online)

Abstract

Intramolecular photocycloaddition of a three-carbon tethered pyrindinone–pyridone system yields the 5-8-5 ring system of the fusicoccin/ophiobolin/ceroplastol families. The stereoselectivity of the cycloaddition was found to be dependent on nitrogen substitution; N-methylation led to exclusively trans products while an absence of nitrogen substitution resulted in solvent-dependent stereoselectivity. Solvent and concentration effects for this cycloaddition were consistent with a hydrogen-bonded dimer that enforces a pro-cis conformation in nonpolar solvents and at higher concentrations. The cis-isomer, a fusicoccin synthesis intermediate, underwent a Cope rearrangement at ambient temperature but could be trapped efficiently as the mono epoxide, yielding a product with six new stereogenic centers. A four-step transformation of an amide carbonyl to a methyl group was achieved using a carbamoyl group to activate the amide for cleavage.

* Dedicated to Howard Zimmerman on the occasion of his 75th birthday


 
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