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External AllACs were directly obtained by methinylation of the parent DACs with formaldehyde in either the racemic or scalemic series. Isomers containing external progargyl and propynyl motifs were also prepared. Internal AllACs were obtained as racemic statistical mixtures of stereoisomers in two steps from the key C<jats:sub>5<\/jats:sub>\u2010DAC <jats:italic>rac<\/jats:italic>\u2010TIPS\u2010C\u2261C\u2010CH(OH)\u2010C\u2261CH and aldehydes. Kinetic resolution of the (<jats:italic>S<\/jats:italic>)\u2010C<jats:sub>5<\/jats:sub>\u2010DAC in 97\u2009%\u2005<jats:italic>ee<\/jats:italic> and (<jats:italic>R<\/jats:italic>)\u2010C<jats:sub>5<\/jats:sub>\u2010DAC in 99\u2009%\u2005<jats:italic>ee<\/jats:italic> was achieved by sequential lipase\u2010mediated acetylation\/hydrolysis using the <jats:italic>Candida antartica<\/jats:italic> lipase (Novozyme 435). The four internal AllAC stereoisomers were prepared by asymmetric methinylation with (<jats:italic>R<\/jats:italic>)\u2010 or (<jats:italic>S<\/jats:italic>)\u2010diphenylprolinol as chiral auxiliary. Cytotoxicity assays on HCT116 cancer cells showed that the most active (eutomeric) external or internal AllAC exhibits an <jats:italic>S<\/jats:italic> configuration, a fatty chain length of <jats:italic>n<\/jats:italic>=12, and a 50\u2009% inhibitory concentration IC<jats:sub>50<\/jats:sub>\u22481.0\u2005\u03bc<jats:sc>m<\/jats:sc>.<\/jats:p>","DOI":"10.1002\/cmdc.201800284","type":"journal-article","created":{"date-parts":[[2018,6,20]],"date-time":"2018-06-20T16:52:33Z","timestamp":1529513553000},"page":"1711-1722","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Methinylogation Approach in Chiral Pharmacophore Design: from Alkynyl\u2010 to Allenyl\u2010carbinol Warheads against Tumor Cells"],"prefix":"10.1002","volume":"13","author":[{"given":"Dymytrii","family":"Listunov","sequence":"first","affiliation":[{"name":"LCC-CNRS Universit\u00e9 de Toulouse, CNRS, UPS  Toulouse France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7264-2681","authenticated-orcid":false,"given":"Etienne","family":"Joly","sequence":"additional","affiliation":[{"name":"UMR CNRS 5089, IPBS (Institut de Pharmacologie et de Biologie Structurale)  205 Route de Narbonne 31077 Toulouse cedex France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Carine","family":"Duhayon","sequence":"additional","affiliation":[{"name":"LCC-CNRS Universit\u00e9 de Toulouse, CNRS, UPS  Toulouse France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nathalie","family":"Saffon\u2010Merceron","sequence":"additional","affiliation":[{"name":"Universit\u00e9 de Toulouse UPS, ICT-FR 2599  31062 Toulouse cedex 9 France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Isabelle","family":"Fabing","sequence":"additional","affiliation":[{"name":"UMR CNRS 5068, LSPCMIB Universit\u00e9 de Toulouse, Universit\u00e9 Paul Sabatier  118 Route de Narbonne 31062 Toulouse cedex 9 France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yves","family":"G\u00e9nisson","sequence":"additional","affiliation":[{"name":"UMR CNRS 5068, LSPCMIB Universit\u00e9 de Toulouse, Universit\u00e9 Paul Sabatier  118 Route de Narbonne 31062 Toulouse cedex 9 France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Val\u00e9rie","family":"Maraval","sequence":"additional","affiliation":[{"name":"LCC-CNRS Universit\u00e9 de Toulouse, CNRS, UPS  Toulouse France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4491-6390","authenticated-orcid":false,"given":"Remi","family":"Chauvin","sequence":"additional","affiliation":[{"name":"LCC-CNRS Universit\u00e9 de Toulouse, CNRS, UPS  Toulouse France"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2018,7,23]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.crci.2008.08.014"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr4006507"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4NP00043A"},{"key":"e_1_2_7_5_1","unstructured":"\u00a0"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)01692-0"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1080\/14786410600906525"},{"key":"e_1_2_7_8_1","unstructured":"\u00a0"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)87828-4"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(96)01037-X"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/np990167"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1080\/10575630008043772"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.3390\/md101046"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/np3008446"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1248\/cpb.c15-00203"},{"key":"e_1_2_7_16_1","unstructured":"\u00a0"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00312a035"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/cmdc.201300230"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2015.08.003"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.5b00494"},{"key":"e_1_2_7_21_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2016.09.001"},{"key":"e_1_2_7_22_2","first-page":"10","volume":"50","author":"Listunov D.","year":"2018","journal-title":"Synthesis"},{"key":"e_1_2_7_23_2","unstructured":"P. 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