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While the closure of the macrocycle by ring closing alkyne metathesis (RCAM) with the aid of a molybdenum alkylidyne complex was high yielding, the envisaged semi\u2010reduction of the cycloalkyne to the corresponding <jats:italic>E<\/jats:italic>\u2010alkene proved challenging. The reasons are likely steric in origin, in that the methyl branches on either side of the alkyne seem to prevent effective coordination of the substrate to the ruthenium catalyst, which must carry a bulky Cp* ligand to ensure high <jats:italic>trans<\/jats:italic>\u2010selectivity. This notion is supported by the preparation of a callyspongiolide analogue, in which the two methyl groups in question are excised; its formation by RCAM followed by <jats:italic>trans<\/jats:italic>\u2010hydrostannation\/proto\u2010destannation was straightforward. In parallel work the formation of the fully functional building block <jats:bold>54<\/jats:bold> showed that the presence of an unprotected \u2010OH group allows even hindered substrates to be processed: the protic group adjacent to the triple bond engages with a chloride ligand on the ruthenium catalyst in hydrogen bonding and hence assists in substrate binding. Moreover, the preparation of an alkynylogous callyspongiolide analogue is described.<\/jats:p>","DOI":"10.1002\/chem.201804987","type":"journal-article","created":{"date-parts":[[2018,11,6]],"date-time":"2018-11-06T04:10:58Z","timestamp":1541477458000},"page":"246-254","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":26,"title":["Synthesis and Molecular Editing of Callyspongiolide, Part 1: The Alkyne Metathesis\/<i>trans<\/i>\u2010Reduction Strategy"],"prefix":"10.1002","volume":"25","author":[{"given":"Guillaume","family":"Mata","sequence":"first","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bernhard","family":"W\u00f6lfl","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0098-3417","authenticated-orcid":false,"given":"Alois","family":"F\u00fcrstner","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2018,12,11]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol403241v"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1038\/sj.onc.1207515"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b03533"},{"key":"e_1_2_7_4_1","unstructured":"\u00a0"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b01523"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6OB02051H"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b13591"},{"key":"e_1_2_7_8_1","unstructured":"For studies towards callyspongiolide see:"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6OB01007E"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b02897"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2018.08.041"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201204513"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201204513"},{"key":"e_1_2_7_13_1","unstructured":"For natural product syntheses via RCAM not yet covered in the recent review [7]see ref.\u2009[9] and the following:"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201501922"},{"key":"e_1_2_7_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201501922"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201512005"},{"key":"e_1_2_7_15_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201512005"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2016.02.050"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b03137"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.5b01312"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201300576"},{"key":"e_1_2_7_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201300576"},{"key":"e_1_2_7_20_1","unstructured":"\u00a0"},{"key":"e_1_2_7_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201301700"},{"key":"e_1_2_7_21_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201301700"},{"key":"e_1_2_7_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201204551"},{"key":"e_1_2_7_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201402550"},{"key":"e_1_2_7_23_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201402550"},{"key":"e_1_2_7_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201500437"},{"key":"e_1_2_7_25_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201510026"},{"key":"e_1_2_7_25_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201510026"},{"key":"e_1_2_7_26_2","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms11300"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.20150317"},{"key":"e_1_2_7_28_1","unstructured":"For failed attempts at using ynoates in RCAM see:"},{"key":"e_1_2_7_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja992074k"},{"key":"e_1_2_7_30_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200802605"},{"key":"e_1_2_7_31_1","unstructured":"\u00a0"},{"key":"e_1_2_7_32_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201302320"},{"key":"e_1_2_7_33_2","unstructured":"see also ref. 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