Directing Biosynthesis VI - Book of abstracts

Daphniphyllum alkaloids biosynthesis Barbara Radzikowska 1 , Benjamin Lichman 1 and William P. Unsworth 2 1 Department of Biology, University of York, UK, 2 Department of Chemistry, University of York, UK Plants from the genus Daphniphyllum have been used in Traditional Chinese Medicines to treat a range of ailments. The medicinal properties of these plants are largely due to unique class of compounds – complex polycyclic alkaloids that exhibit a range of bioactivities, including anticancer, insecticidal and vasorelaxatory properties 1 . The understanding of alkaloid biosynthesis will give us access to the Daphniphyllum alkaloids to further study their bioactivities as well as develop novel enzymatic routes to complex, bioactive compounds and inspire new synthetic chemical approaches to compounds with multiple fused rings 2 . Prior studies have shown that Daphniphyllum alkaloids are likely derived from the isoprenoid squalene 3 that undergoes sequential oxidation to dialdehyde 2 , transamination and cyclisation to form proto-daphniphylline 3 , a hypothesised precursor to Daphniphyllum alkaloids (shown below). The proposed enzyme catalysing those reactions (proto-daphniphylline synthase) and the reaction mechanism are still unknown. In order to discover and characterise proto-daphniphylline synthase, dialdehyde 2 is required. Therefore, the presented work will discuss the current progress towards the synthesis of compound 2 , which will be used to enter the biosynthetic pathway and identify the proto-daphniphylline synthase. Once the substrate is synthesised, it will be used in functional assays to identify active enzymes involved in the biosynthesis. Additionally, Daphniphyllum alkaloids have been isolated from leaves of Daphniphyllum macropodum and they will be used as standards in the future work.

References 1. H. Heathcock, S. K. Davidsen, S. Mills and M. A. Sanner, J. Am. Chem. Soc , 1986, 108 , 5651–5652. 2. E. C. Cherney, P. S. Baran, Isr. Chem., 2011, 51 , 391–405. 3. R. B. Ruggeri and C. H. Heathcock, Pure Appl. Chem. , 1989, 61 , 289–292.

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