Photochemically Generated Building Blocks I

The Tricyclooctanone Approach to Polyquinane Syntheses Part I: The Underlying Photochemistry
  • Kurt Schaffner
  • Martin Demuth
Part of the Modern Synthetic Methods book series (MOD.SYNTH., volume 4)

Abstract

The results of the mechanistic investigations of the photochemical 1, 3-acyl shift and oxadi-π-methane reactions of βγ—unsaturated ketones are summarized, and the use of the latter reaction as a key step in the total syntheses of enantiomerically pure natural polyquinane products is reviewed. The triplet-sensitized oxadi-π-methane rearrangement of the readily accessible pure enantiomers of bicyclo[2.2.2]oct-5-en-2-one affords the polyvalent enantiomeric tricyclo[3.3.0.02,B]octan-3-one building blocks (Section 3.1.). Under the same irradiation conditions, in the presence of hydrogen donors, the 1-methoxybicyclooctenones are transformed, via the corresponding tricyclooctanones, into bicyclo[3.3.0]octane-3,6-diones (Section 3.2.). Further, more target-oriented, extensions of the tricyclooctanone approach include the rearrangements of the epimeric 2,2,5-trimethylbicyclo [2.2.2]oct-ene-3,6-diones (Section 3.3.) and of a tricyclo-[5.2.2.03,7]undec-8-en-10-one (Section 3.4.). All photoreactions described proceed with high chemical and quantum yields on preparative scale.

Keywords

Quantum Yield Direct Excitation Methyl Ketone Triplet Energy Unsaturated Ketone 
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Copyright information

© Springer-Verlag Berlin Heidelberg 1986

Authors and Affiliations

  • Kurt Schaffner
    • 1
  • Martin Demuth
    • 1
  1. 1.Max-Planck-Institut für StrahlenchemieMülheim, a.d. RuhrDeutschland

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