{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,11]],"date-time":"2026-09-11T16:52:31Z","timestamp":1789145551589,"version":"build-2803163510"},"reference-count":131,"publisher":"Wiley","issue":"11","license":[{"start":{"date-parts":[[2022,1,10]],"date-time":"2022-01-10T00:00:00Z","timestamp":1641772800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100004189","name":"Max-Planck-Gesellschaft","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100004189","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2022,2,21]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The total synthesis of the 16\u2010membered macrolide mycinamicin IV is outlined, which complements our previously disclosed, largely catalysis\u2010based route to the aglycone. This work must also be seen in the context of our recent conquest of aldgamycin N, a related antibiotic featuring a similar core but a distinctly different functionalization pattern. Taken together, these projects prove that the underlying blueprint is integrative and hence qualifies for a collective approach to this prominent class of natural products. In both cases, the final glycosylation phase mandated close attention and was accomplished only after robust de novo syntheses of the (di)deoxy sugars of the desosamine, chalcose, mycinose and aldgarose types had been established. Systematic screening of the glycosidation promoter was also critically important for success.<\/jats:p>","DOI":"10.1002\/chem.202104400","type":"journal-article","created":{"date-parts":[[2021,12,15]],"date-time":"2021-12-15T06:12:25Z","timestamp":1639548745000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Total Synthesis of Mycinamicin IV as Integral Part of a Collective Approach to Macrolide Antibiotics"],"prefix":"10.1002","volume":"28","author":[{"given":"Georg","family":"Sp\u00e4th","sequence":"first","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":[[2022,1,10]]},"reference":[{"key":"e_1_2_3_1_1","unstructured":"\u00a0"},{"key":"e_1_2_3_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00653"},{"key":"e_1_2_3_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c08920"},{"key":"e_1_2_3_4_1","unstructured":"For leading references see the following and literature cited therein:"},{"key":"e_1_2_3_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c06450"},{"key":"e_1_2_3_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202101766"},{"key":"e_1_2_3_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202101766"},{"key":"e_1_2_3_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.1c00056"},{"key":"e_1_2_3_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201914042"},{"key":"e_1_2_3_8_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201914042"},{"key":"e_1_2_3_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202009238"},{"key":"e_1_2_3_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202009238"},{"key":"e_1_2_3_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b04053"},{"key":"e_1_2_3_11_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2825"},{"key":"e_1_2_3_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201704628"},{"key":"e_1_2_3_12_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201704628"},{"key":"e_1_2_3_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar5004303"},{"key":"e_1_2_3_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja509329x"},{"key":"e_1_2_3_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201202643"},{"key":"e_1_2_3_15_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201202643"},{"key":"e_1_2_3_16_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature10232"},{"key":"e_1_2_3_17_1","unstructured":"For examples from this laboratory see:"},{"key":"e_1_2_3_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202015243"},{"key":"e_1_2_3_18_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202015243"},{"key":"e_1_2_3_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202011472"},{"key":"e_1_2_3_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202011472"},{"key":"e_1_2_3_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c07955"},{"key":"e_1_2_3_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c01700"},{"key":"e_1_2_3_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201501491"},{"key":"e_1_2_3_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201005850"},{"key":"e_1_2_3_23_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201005850"},{"key":"e_1_2_3_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201300393"},{"key":"e_1_2_3_25_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201100180"},{"key":"e_1_2_3_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200802067"},{"key":"e_1_2_3_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200601135"},{"key":"e_1_2_3_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200600592"},{"key":"e_1_2_3_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0617800"},{"key":"e_1_2_3_30_1","unstructured":"\u00a0"},{"key":"e_1_2_3_31_2","doi-asserted-by":"publisher","DOI":"10.7164\/antibiotics.34.346"},{"key":"e_1_2_3_32_2","doi-asserted-by":"publisher","DOI":"10.7164\/antibiotics.34.1075"},{"key":"e_1_2_3_33_2","doi-asserted-by":"publisher","DOI":"10.7164\/antibiotics.33.364"},{"key":"e_1_2_3_34_1","doi-asserted-by":"publisher","DOI":"10.7164\/antibiotics.42.1003"},{"key":"e_1_2_3_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jnatprod.6b00200"},{"key":"e_1_2_3_36_1","unstructured":"For other aldgamycins see:"},{"key":"e_1_2_3_37_2","first-page":"87","volume":"10","author":"Kunstmann M. P.","year":"1964","journal-title":"Antimicrob. Agents Chemother."},{"key":"e_1_2_3_38_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)97899-8"},{"key":"e_1_2_3_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19751080311"},{"key":"e_1_2_3_40_2","doi-asserted-by":"publisher","DOI":"10.7164\/antibiotics.39.1776"},{"key":"e_1_2_3_41_2","doi-asserted-by":"publisher","DOI":"10.1038\/ja.2009.6"},{"key":"e_1_2_3_42_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202016475"},{"key":"e_1_2_3_42_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202016475"},{"key":"e_1_2_3_43_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202016477"},{"key":"e_1_2_3_43_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202016477"},{"key":"e_1_2_3_44_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature17967"},{"key":"e_1_2_3_45_1","doi-asserted-by":"publisher","DOI":"10.1002\/slct.201803591"},{"key":"e_1_2_3_46_1","unstructured":"For the only previous total synthesis of mycinamicin IV and VII see:"},{"key":"e_1_2_3_47_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.1987.113"},{"key":"e_1_2_3_48_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(88)85296-1"},{"key":"e_1_2_3_49_1","unstructured":"Protomycinolide IV:"},{"key":"e_1_2_3_50_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)91187-6"},{"key":"e_1_2_3_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00277a028"},{"key":"e_1_2_3_52_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198610281"},{"key":"e_1_2_3_52_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19860981121"},{"key":"e_1_2_3_53_1","unstructured":"For the synthesis of various fragments see:"},{"key":"e_1_2_3_54_2","doi-asserted-by":"publisher","DOI":"10.1002\/jlac.199019900103"},{"key":"e_1_2_3_55_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1992-21289"},{"key":"e_1_2_3_56_2","doi-asserted-by":"publisher","DOI":"10.3987\/COM-91-S79"},{"key":"e_1_2_3_57_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2005.698"},{"key":"e_1_2_3_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja5071202"},{"key":"e_1_2_3_59_1","unstructured":"\u00a0"},{"key":"e_1_2_3_60_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201108203"},{"key":"e_1_2_3_60_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201108203"},{"key":"e_1_2_3_61_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b09164"},{"key":"e_1_2_3_62_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201811888"},{"key":"e_1_2_3_62_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201811888"},{"key":"e_1_2_3_63_1","unstructured":"\u00a0"},{"key":"e_1_2_3_64_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201507151"},{"key":"e_1_2_3_64_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201507151"},{"key":"e_1_2_3_65_2","first-page":"29","volume":"47","author":"Wong G. W.","year":"2014","journal-title":"Aldrichimica Acta"},{"key":"e_1_2_3_66_1","unstructured":"A total synthesis of ambruticin features the arguably most advanced example of an asymmetric hydroformylation; in this case however a 1 3-diene was used which has an inherently higher bias for branch-selectivity than an ordinary terminal alkene because the reaction passes through a favorable allylrhodium intermediate:"},{"key":"e_1_2_3_67_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja016893s"},{"key":"e_1_2_3_68_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol300194x"},{"key":"e_1_2_3_69_1","unstructured":"Asymmetric hydroformylation of simple acrolein acetals and acrylic acid orthoesters were used to prepare some building blocks for the syntheses of dictyostatin and the Prelog-Djerassi lactone see:"},{"key":"e_1_2_3_70_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201302565"},{"key":"e_1_2_3_70_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201302565"},{"key":"e_1_2_3_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol3008765"},{"key":"e_1_2_3_72_1","unstructured":"The free alcohol5(R=H) also gave appreciable amounts of the desired branched aldehyde which exists exclusively in lactol from. Further attempts at optimizing this promising result were eventually discontinued when we noticed that this lactol failed to react with alkynylmetal reagents derived from enyne13under a variety of conditions and a detour would have been necessary to overcome this impasse. More elaborate auxiliaries covalently attached to the hydroxy group known to favor the branched product (Ph2PO\u2212 o-(Ph2P)C6H4COO\u2212) proved impractical and partly unstable and were hence disregarded. Amongst the \u201cordinary\u201d protecting groups the MOM-acetal gave by far the best results."},{"key":"e_1_2_3_73_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.0c00759"},{"key":"e_1_2_3_74_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b09782"},{"key":"e_1_2_3_75_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201701391"},{"key":"e_1_2_3_75_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201701391"},{"key":"e_1_2_3_76_1","unstructured":"\u00a0"},{"key":"e_1_2_3_77_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b01475"},{"key":"e_1_2_3_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b12517"},{"key":"e_1_2_3_79_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201601163"},{"key":"e_1_2_3_80_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)99693-5"},{"key":"e_1_2_3_81_1","doi-asserted-by":"publisher","DOI":"10.1038\/ja.2017.116"},{"key":"e_1_2_3_82_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201507357"},{"key":"e_1_2_3_82_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201507357"},{"key":"e_1_2_3_83_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.carres.2007.10.004"},{"key":"e_1_2_3_84_1","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19990816)38:16<2398::AID-ANIE2398>3.0.CO;2-E"},{"key":"e_1_2_3_84_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19990816)111:16<2549::AID-ANGE2549>3.0.CO;2-H"},{"key":"e_1_2_3_85_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00347a053"},{"key":"e_1_2_3_86_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)96443-9"},{"key":"e_1_2_3_87_1","first-page":"313","volume-title":"Preparative Carbohydrate Chemistry","author":"Nicolaou K. C.","year":"1997"},{"key":"e_1_2_3_88_1","unstructured":"\u00a0"},{"key":"e_1_2_3_89_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198602121"},{"key":"e_1_2_3_89_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19860980305"},{"key":"e_1_2_3_90_2","first-page":"283","volume-title":"Preparative Carbohydrate Chemistry","author":"Schmidt R. R.","year":"1997"},{"key":"e_1_2_3_91_1","volume-title":"Macrolide Antibiotics. Chemistry, Biology and Practice","author":"Omura S."},{"key":"e_1_2_3_92_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200600350"},{"key":"e_1_2_3_92_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200600350"},{"key":"e_1_2_3_93_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CS00426D"},{"key":"e_1_2_3_94_1","unstructured":"Degradation of erythromycin followed by two chemical steps is the shortest route cf. Ref.\u2005[27]; the shortest known purely chemical approach comprises four steps to free desosamine followed by two steps for its functionalization cf. [28 \u200929]."},{"key":"e_1_2_3_95_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b13766"},{"key":"e_1_2_3_96_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00195a007"},{"key":"e_1_2_3_97_1","unstructured":"For use in total synthesis from this laboratory see Ref.\u2005[3d] and the following:"},{"key":"e_1_2_3_98_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja508846g"},{"key":"e_1_2_3_99_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201404873"},{"key":"e_1_2_3_100_1","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(88)85295-X"},{"key":"e_1_2_3_101_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol9908068"},{"key":"e_1_2_3_102_1","unstructured":"The stereochemical outcome was independent of whether the \u03b1- or the \u03b2-anomer of glycosyl fluoride39\u2009awas used."},{"key":"e_1_2_3_103_1","unstructured":"For precedent showing that high dilution can favor \u03b2-glycoside formation with glycosyl donors devoid of \u201cparticipating\u201d 2-acyl substituents see:"},{"key":"e_1_2_3_104_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200901119"},{"key":"e_1_2_3_105_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201100732"},{"key":"e_1_2_3_106_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-1990-21214"},{"key":"e_1_2_3_107_1","unstructured":"For previous exploitation of this effect in total synthesis by our laboratory see:"},{"key":"e_1_2_3_108_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja027346p"},{"key":"e_1_2_3_109_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja036521e"},{"key":"e_1_2_3_110_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo035079f"},{"key":"e_1_2_3_111_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200305588"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202104400","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/chem.202104400","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202104400","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T11:17:59Z","timestamp":1760267879000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.202104400"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,1,10]]},"references-count":131,"journal-issue":{"issue":"11","published-print":{"date-parts":[[2022,2,21]]}},"alternative-id":["10.1002\/chem.202104400"],"URL":"https:\/\/doi.org\/10.1002\/chem.202104400","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,1,10]]},"assertion":[{"value":"2021-12-09","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2022-01-10","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202104400"}}