Illustrating the power of singlet oxygen chemistry in a synthetic context: biomimetic syntheses of litseaverticillols A-G, I and J and the structural reassignment of litseaverticillol E.
Biomimetic syntheses of the litseaverticillols A-G, I and J are reported herein. The syntheses rely heavily on the application of two different modes of reaction for photochemically generated singlet oxygen, namely, the [4+2] cycloaddition of singlet oxygen (1O2) with furans and the ene reaction of 1O2 with double bonds. The highlight of these syntheses is a one-pot cascade sequence, involving five synthetic operations initiated by a [4+2] reaction, to form the fully functionalised litseaverticillol core. A series of regioselective ene reactions are then used to appositely functionalise the side chains. The synthesis of litseaverticillol E (both its originally proposed and its actual structures) allows a structural reassignment of this natural product.
Vassilikogiannakis
Georgios
G
Department of Chemistry, University of Crete, 71409 Iraklion, Crete, Greece. vasil@chemistry.uoc.gr
Margaros
Ioannis
I
Montagnon
Tamsyn
T
Stratakis
Manolis
M
D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D018716:Molecular Mimicry; D015394:Molecular Structure; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry*; D026082:Singlet Oxygen / Q000737:chemistry*
D012717:Sesquiterpenes; D026082:Singlet Oxygen