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Specifically, an iridium\u2010catalyzed two\u2010directional Krische allylation and a cobalt\u2010catalyzed carbonylative epoxide opening served as convenient entry points for the preparation of the major building blocks. The final stages feature the first implementation of terminal\u2010acetylene metathesis into natural product synthesis, which is remarkable as this class of substrates was beyond reach until very recently; key to success was the use of the highly selective molybdenum alkylidyne complex <jats:bold>42<\/jats:bold> as the catalyst. Although the constitution and stereochemistry of the synthetic samples are unambiguous, the spectra of <jats:bold>1<\/jats:bold> as well as of 11\u2010<jats:italic>epi<\/jats:italic>\u2010<jats:bold>1<\/jats:bold> deviate from those of the natural product, which implies a subtle but deep\u2010seated error in the original structure assignment.<\/jats:p>","DOI":"10.1002\/anie.201400605","type":"journal-article","created":{"date-parts":[[2014,3,12]],"date-time":"2014-03-12T12:44:25Z","timestamp":1394628265000},"page":"4217-4221","source":"Crossref","is-referenced-by-count":114,"title":["Catalysis\u2010Based Total Synthesis of Putative Mandelalide\u2005A"],"prefix":"10.1002","volume":"53","author":[{"given":"Jens","family":"Willwacher","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alois","family":"F\u00fcrstner","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2014,3,12]]},"reference":[{"key":"e_1_2_2_1_2","unstructured":"C.\u2005A. Kuttruff M.\u2005D. Eastgate P.\u2005S. Baran Nat. Prod. Rep.\u00ad2014 DOI:."},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo3008622"},{"key":"e_1_2_2_3_2","unstructured":"Compound\u20051 as the most active member shows IC50values of 12\u2005nMand 44\u2005nMfor the NCI\u2010H460 and Neuro\u20102A cell lines respectively; see Ref.\u2005[2]."},{"key":"e_1_2_2_4_2","unstructured":"\u00a0"},{"key":"e_1_2_2_5_2","unstructured":"P.\u2005L. Winder Ph.D. Thesis Florida Atlantic University 2009; for a study towards2and a structural discussion see:"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol400280b"},{"key":"e_1_2_2_7_2","unstructured":"As1derives from an ascidian whereas2was isolated from a sponge it is not unreasonable to assume that the actual producers of these compounds are (bacterial) symbionts."},{"key":"e_1_2_2_8_2","unstructured":"However madeirolide\u2005A was reported to be strongly fungicidal; see Ref.\u2005[4]."},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201204513"},{"key":"e_1_2_2_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201204513"},{"key":"e_1_2_2_10_2","unstructured":"\u00a0"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19980619)110:12<1758::AID-ANGE1758>3.0.CO;2-I"},{"key":"e_1_2_2_11_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19980703)37:12<1734::AID-ANIE1734>3.0.CO;2-6"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja992074k"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1229713"},{"key":"e_1_2_2_14_2","unstructured":"\u00a0"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201200621"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja104800w"},{"key":"e_1_2_2_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201207772"},{"key":"e_1_2_2_17_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201207772"},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201302320"},{"key":"e_1_2_2_19_2","unstructured":"\u00a0"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja204570w"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200901648"},{"key":"e_1_2_2_21_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200901648"},{"key":"e_1_2_2_22_2","unstructured":"The minor isomer was recycled to diol4on treatment with activated zinc in DMA (80\u2009%)."},{"key":"e_1_2_2_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja970402f"},{"key":"e_1_2_2_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0214882"},{"key":"e_1_2_2_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00237a081"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9703360"},{"key":"e_1_2_2_27_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(97)01462-7"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc17070a"},{"key":"e_1_2_2_29_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200290021"},{"key":"e_1_2_2_29_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200290022"},{"key":"e_1_2_2_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo0057497"},{"key":"e_1_2_2_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja206230h"},{"key":"e_1_2_2_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja200712f"},{"key":"e_1_2_2_33_2","unstructured":"Z.\u2010Y.Zhan PCT WO 2007\/003135A1 2007."},{"key":"e_1_2_2_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00173a071"},{"key":"e_1_2_2_35_2","unstructured":"\u00a0"},{"key":"e_1_2_2_36_2","first-page":"2310","author":"Ralston K. 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