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The Total Synthesis of Thapsigargin

The Total Synthesis of Thapsigargin

Klemens Högenauer (ORCID: )
  • Grant DOI 10.55776/J1999
  • Funding program Erwin Schrödinger
  • Status ended
  • Start January 30, 2001
  • End January 30, 2002
  • Funding amount € 29,796

Disciplines

Chemistry (100%)

Keywords

    THAPSIGARGIN, TOTAL SYNTHESIS, SERCA INHIBITOR

Abstract

The natural product thapsigargin, a plant extract from Thapsia garnica L., was shown to have an important biological profile, namely its ability to induce cell death of prostate cancer cell lines at nanomolecular concentrations. This activity and the challenge of creating its highly functionalised structure (tricyclic backbone with 8 stereogenic centres, 4 different and densely packed ester groups, 2 tertiary alkohols and a gamma-lactone) make this molecule an interesting target for total synthesis. The proposed route to the first total synthesis of thapsigargin is highly flexible and should furthermore allow the synthesis of labelled derivatives and analogues for metabolic studies and biological testing. The C1-C5 cyclopentane is planned to be derived from enantiomerically pure carvone, featuring a stereoselective Favorskii rearrangement as a key step. Addition of a second fragment by cuprate addition and some functional group manipulation should reveal the precursor for the second key feature, a Prins cyclisation, to furnish the [3.5.0] ring system. A directed dihydroxylation is expected to introduce the remaining alkohol functionalities and enolate manipulation of the ketone at C3 should establish the desired structural pattern. Applying this strategy, analogues of the natural product would be accessible, allowing further investigations of structure activity relationships and metabolical studies.

Research institution(s)
  • Universität Wien - 10%
  • University of Cambridge - 100%

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