Photochemical relationships in Sacoglossan polypropionates.
Cyercene A has been synthesized and converted to placidene A and isoplacidene A through photoisomerization with sunlight. Hydroperoxide, isolated form Placida dendritica, was synthesized both by singlet oxygenation of cyercene A using Rose Bengal and through the irradiation of cyercene A alone in aerobic solution. The observation that hydroperoxide could be made by singlet oxygenation of cyercene A and that this occurs when cyercene A alone is irradiated supported the hypothesis that gamma-pyrones may act as triplet sensitizers. This was confirmed using cyercene A and a model gamma-pyrone to sensitize the photooxidation of n-butyl sulfide. The biosynthetic implications of these observations for Sacoglossan polypropionates are discussed.
Zuidema
Daniel R
DR
Department of Chemistry, Wake Forest University, Winston-Salem, North Carolina 27109, USA.
Jones
Paul B
PB
D000818:Animals; D002384:Catalysis; D007202:Indicators and Reagents; D015394:Molecular Structure; D008974:Mollusca / Q000737:chemistry*; D019906:Nuclear Magnetic Resonance, Biomolecular; D010084:Oxidation-Reduction; D010777:Photochemistry; D011422:Propionates / Q000737:chemistry*; D011753:Pyrones / Q000138:chemical synthesis* / Q000737:chemistry*; D012395:Rose Bengal; D013472:Sunlight
D007202:Indicators and Reagents; D011422:Propionates; D011753:Pyrones; C501019:cyercene A; C501020:placidene A; D012395:Rose Bengal