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Total synthesis of dehaloperophoramidine using a highly diastereoselective Hosomi-Sakurai reaction
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dc.contributor.author | Wilkie, Ross Philip | |
dc.contributor.author | Neal, Andrew | |
dc.contributor.author | Johnston, Craig Andrew | |
dc.contributor.author | Voûte, Nicholas | |
dc.contributor.author | Lancefield, Christopher Stuart | |
dc.contributor.author | Stell, Matthew | |
dc.contributor.author | Medda, Federico | |
dc.contributor.author | Makiyi, Edward Frank | |
dc.contributor.author | Turner, Emma | |
dc.contributor.author | Ojo, Oluwarotimi Stephen | |
dc.contributor.author | Slawin, Alexandra Martha Zoya | |
dc.contributor.author | Lebl, Tomas | |
dc.contributor.author | Mullen, Peter | |
dc.contributor.author | Harrison, David James | |
dc.contributor.author | Ireland, Chris M | |
dc.contributor.author | Westwood, Nicholas James | |
dc.date.accessioned | 2016-08-19T09:40:14Z | |
dc.date.available | 2016-08-19T09:40:14Z | |
dc.date.issued | 2016-09-14 | |
dc.identifier | 244841236 | |
dc.identifier | 4eac4de0-903e-4c77-9db8-17c4b51deed3 | |
dc.identifier | 84984693637 | |
dc.identifier | 000382122200008 | |
dc.identifier.citation | Wilkie , R P , Neal , A , Johnston , C A , Voûte , N , Lancefield , C S , Stell , M , Medda , F , Makiyi , E F , Turner , E , Ojo , O S , Slawin , A M Z , Lebl , T , Mullen , P , Harrison , D J , Ireland , C M & Westwood , N J 2016 , ' Total synthesis of dehaloperophoramidine using a highly diastereoselective Hosomi-Sakurai reaction ' , Chemical Communications , vol. 52 , no. 71 , pp. 10747-10750 . https://doi.org/10.1039/c6cc05747k | en |
dc.identifier.issn | 1359-7345 | |
dc.identifier.other | ORCID: /0000-0002-0269-3221/work/48131737 | |
dc.identifier.other | ORCID: /0000-0003-0630-0138/work/56424154 | |
dc.identifier.other | ORCID: /0000-0002-9527-6418/work/56861554 | |
dc.identifier.other | ORCID: /0000-0001-9041-9988/work/64034227 | |
dc.identifier.other | ORCID: /0000-0002-0841-609X/work/157141032 | |
dc.identifier.uri | https://hdl.handle.net/10023/9333 | |
dc.description | The authors would like to acknowledge EPSRC for PhD funding through the Doctoral Training Schemes. | en |
dc.description.abstract | The synthesis of dehaloperophoramidine, a non-halogenated derivative of the marine natural product perophoramidine, is reported. The key steps included a [3,3]-Claisen rearrangement and an epoxide opening/allylsilylation (modified Hosomi-Sakurai) reaction to install the contiguous all-carbon quaternary stereocentres with the required relative stereochemistry. The first five steps were carried out on seventy gram scale without the need for chromatography. Resolution of the [3,3]-Claisen product gave samples of the highly enantiomerically-enriched ketones which are flexible starting points for the synthesis of a number of complex ring structures. A regio- and diastereo-selective iodocyclisation was then used to differentiate between two allyl groups enabling the synthesis of the target molecule by two different routes. A detailed comparison of the trifluoroacetic acid salt of the synthetic dehaloperophoramidine with authentic material was carried out including a key doping experiment. Biological testing showed that (±)-dehaloperophoramidine was cytotoxic to HCT116, HT29 and LoVo colorectal carcinoma cells with comparable activity to that reported for the halogenated perophoramidine. This demonstrated for the first time that the halogens are not essential for the biological activity of this alkaloid class. | |
dc.format.extent | 1960417 | |
dc.language.iso | eng | |
dc.relation.ispartof | Chemical Communications | en |
dc.subject | QD Chemistry | en |
dc.subject | DAS | en |
dc.subject | SDG 14 - Life Below Water | en |
dc.subject.lcc | QD | en |
dc.title | Total synthesis of dehaloperophoramidine using a highly diastereoselective Hosomi-Sakurai reaction | en |
dc.type | Journal article | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.contributor.institution | University of St Andrews. School of Medicine | en |
dc.contributor.institution | University of St Andrews. Biomedical Sciences Research Complex | en |
dc.identifier.doi | 10.1039/c6cc05747k | |
dc.description.status | Peer reviewed | en |
dc.identifier.url | http://www.rsc.org/suppdata/c6/cc/c6cc05747k/c6cc05747k1.pdf | en |
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