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Further model studies emphasise the importance of the cyano
substituent in controlling both the yield and regioselective
outcome of the intramolecular dipolar cycloaddition under ther-
modynamic control, leading preferentially to the required 6,6,5-
spirocyclic isoxazolidine cycloadducts.
Application of the knowledge from these model studies
enabled these domino cycloreversion–cycloaddition processes to
be used to construct the core spirocyclic precursors to the natu-
rally occurring histrionicotoxin alkaloids, HTX-259A (2),
HTX-285C (3) and HTX-285E (4).
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Acknowledgements
We thank EPSRC (studentships to SDR and CJS), BBSRC
(studentship to AJH) and Syngenta (CASE award to AJH),
GlaxoSmithKline (CASE Award to SDR) and Novartis (CASE
Award to CJS) as well as CSIRO Office of the Chief Executive
and CSIRO Division of Materials Science and Engineering for
supporting this work.
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