Polycyclic ethers and an unexpected dearomatisation reaction during studies towards the bioactive alkaloid, perophoramidine
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The bioactive alkaloid natural product perophoramidine and the related family of compounds known as the communesins have inspired the synthesis community for more than a decade. Many of the elegant approaches have required the synthesis of complex intermediates that have not always reacted in the expected manner. In this study we describe a series of cyclic ether-containing precursors that were prepared during our synthetic studies towards these natural products. Attempts to open the cyclic ether ring and trap the resulting stabilised carbocation with a carbon nucleophile ultimately led to the preparation of a diallyl-substituted all carbon quaternary centre. Subsequent attempts to differentiate between the two allyl groups resulted in a relatively clean transformation to an unexpected compound. Extensive structural characterisation, including small molecule X-ray crystallography, showed that a dearomatisation reaction had occurred.
Johnston , C A , Wilkie , R P , Krauss , H , Neal , A R , Slawin , A M Z , Lebl , T & Westwood , N J 2018 , ' Polycyclic ethers and an unexpected dearomatisation reaction during studies towards the bioactive alkaloid, perophoramidine ' , Tetrahedron , vol. 74 , no. 26 , pp. 3339-3347 . https://doi.org/10.1016/j.tet.2018.04.086
© 2018 Elsevier Ltd. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1016/j.tet.2018.04.086
DescriptionWe would like to acknowledge EPSRC for PhD funding through the Doctoral Training Schemes and the EPSRC National Mass Spectrometry Service Centre, Swansea for mass spectrometric analysis.
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