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

Kevin F. McGee Jr.; Taleb H. Al-Tel; Scott McN. Sieburth

doi:10.1055/s-2001-15066

Synthesis, Table of Contents

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^[*]

Authors

Kevin F. McGee Jr.

¹Department of Chemistry, State University of New York, Stony Brook, New York 11794–3400, USA
Taleb H. Al-Tel

¹Department of Chemistry, State University of New York, Stony Brook, New York 11794–3400, USA
Scott McN. Sieburth

¹Department of Chemistry, State University of New York, Stony Brook, New York 11794–3400, USA

Abstract

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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.

Key words

fusicoccin - higher-order cycloadditions - photochemistry - stereoselectivity - solvent effects

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References

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

Authors

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