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DOI: 10.1055/s-2001-15066
Fusicoccin Synthesis by Intramolecular [4+4] Photocycloaddition of 2-Pyridones: Stereocontrol of the Cycloaddition and Elaboration of the Pentacyclic Product[*]
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.
Key words
fusicoccin - higher-order cycloadditions - photochemistry - stereoselectivity - solvent effects* Dedicated to Howard Zimmerman on the occasion of his 75th birthday
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References
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2 Current address: An-Najah National University, Nablus, Palestine.
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