{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,12]],"date-time":"2026-09-12T15:27:20Z","timestamp":1789226840827,"version":"build-2803163510"},"reference-count":188,"publisher":"Wiley","issue":"25","license":[{"start":{"date-parts":[[2016,5,20]],"date-time":"2016-05-20T00:00:00Z","timestamp":1463702400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"name":"MPG"},{"name":"Fonds der Chemischen Industrie"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2016,6,13]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Although molybdenum alkylidyne complexes such as <jats:bold>1<\/jats:bold> endowed with triarylsilanolate ligands are excellent catalysts for alkyne metathesis, they can encounter limitations when (multiple) protic sites are present in a given substrate and\/or when forcing conditions are necessary. In such cases, a catalyst formed in situ upon mixing of the trisamidomolybenum alkylidyne complex <jats:bold>3<\/jats:bold> and the readily available trisilanol derivatives <jats:bold>8<\/jats:bold> or <jats:bold>11<\/jats:bold> shows significantly better performance. This two\u2010component system worked well for a series of model compounds comprising primary, secondary or phenolic \u2010OH groups, as well as for a set of challenging (bis)propargylic substrates. Its remarkable efficiency is also evident from applications to the total syntheses of manshurolide, a highly strained sesquiterpene lactone with kinase inhibitory activity, and the structurally demanding immunosuppressive cyclodiyne ivorenolide A; in either case, the standard catalyst <jats:bold>1<\/jats:bold> largely failed to effect the critical macrocyclization, whereas the two\u2010component system was fully operative. A study directed toward the quinolizidine alkaloid lythrancepine I features yet another instructive example, in that a triyne substrate was metathesized with the help of <jats:bold>3<\/jats:bold>\/<jats:bold>11<\/jats:bold> such that two of the triple bonds participated in ring closure, while the third one passed uncompromised. As a spin\u2010off of this project, a much improved ruthenium catalyst for the redox isomerization of propargyl alcohols to the corresponding enones was developed.<\/jats:p>","DOI":"10.1002\/chem.201601163","type":"journal-article","created":{"date-parts":[[2016,5,21]],"date-time":"2016-05-21T19:58:56Z","timestamp":1463860736000},"page":"8494-8507","source":"Crossref","is-referenced-by-count":100,"title":["A Two\u2010Component Alkyne Metathesis Catalyst System with an Improved Substrate Scope and Functional Group Tolerance: Development and Applications to Natural Product Synthesis"],"prefix":"10.1002","volume":"22","author":[{"given":"Sebastian","family":"Schaubach","sequence":"first","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Konrad","family":"Gebauer","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Felix","family":"Ungeheuer","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Laura","family":"Hoffmeister","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marina K.","family":"Ilg","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Conny","family":"Wirtz","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr 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situation did not change when yet other trisilanols with shorter or longer tethers between the silanol groups were used; S. Schaubach projected doctoral thesis TU Dortmund."},{"key":"e_1_2_6_68_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0103726"},{"key":"e_1_2_6_69_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200600085"},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200600085"},{"key":"e_1_2_6_70_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201402550"},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201402550"},{"key":"e_1_2_6_71_1","unstructured":"\u00a0"},{"key":"e_1_2_6_72_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201206670"},{"key":"e_1_2_6_72_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201206670"},{"key":"e_1_2_6_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja508846g"},{"key":"e_1_2_6_74_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201501608"},{"key":"e_1_2_6_74_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201501608"},{"key":"e_1_2_6_75_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201501765"},{"key":"e_1_2_6_76_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201510026"},{"key":"e_1_2_6_76_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201510026"},{"key":"e_1_2_6_77_1","unstructured":"Such mixtures were previously used in material science see:"},{"key":"e_1_2_6_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja303572k"},{"key":"e_1_2_6_79_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja204795q"},{"key":"e_1_2_6_80_2","doi-asserted-by":"publisher","DOI":"10.1039\/C3SC52018H"},{"key":"e_1_2_6_81_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma500673x"},{"key":"e_1_2_6_82_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-0031-1290503"},{"key":"e_1_2_6_83_1","unstructured":"The published X-ray data do not allow for an unambiguous assignment of the absolute configuration; we thank Prof.\u2005C.\u2005W. 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