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To mitigate the \u201ccost\u201d of this strategic amendment, a practical and scalable de novo synthesis of this branched octose was developed. The glycoside formation required mild conditions; it commenced with the reaction of the aglycone with the trichloroacetimidate donor to give a transient orthoester, which slowly rearranged to the desired aldgaropyranoside. The presence of the polar peripheral groups in the product did not impede the selective late\u2010stage functionalization of the macrolide ring itself: the contained propargylic alcohol entity was readily transformed into the characteristic acyloin motif of the target by a ruthenium\u2010catalyzed <jats:italic>trans<\/jats:italic>\u2010hydrostannation followed by a modified Chan\u2010Lam\u2010type coupling.<\/jats:p>","DOI":"10.1002\/anie.202016477","type":"journal-article","created":{"date-parts":[[2021,1,15]],"date-time":"2021-01-15T23:36:46Z","timestamp":1610753806000},"page":"7900-7905","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Scalable De Novo Synthesis of Aldgarose and Total Synthesis of Aldgamycin\u2005N"],"prefix":"10.1002","volume":"60","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":[[2021,3,3]]},"reference":[{"key":"e_1_2_6_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202016475"},{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202016475"},{"key":"e_1_2_6_2_1","unstructured":"\u00a0"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.7164\/antibiotics.34.346"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.7164\/antibiotics.34.1075"},{"key":"e_1_2_6_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jnatprod.6b00200"},{"key":"e_1_2_6_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/slct.201803591"},{"key":"e_1_2_6_7_1","unstructured":"Similar problems of transannular interference are known for several other 16-membered macrolide antibiotics including erythromycin\u2005B; for representative cases see the following:"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo01282a051"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo201319b"},{"key":"e_1_2_6_10_1","unstructured":"\u00a0"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.197210211"},{"key":"e_1_2_6_11_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19720842205"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19741070922"},{"key":"e_1_2_6_13_1","unstructured":"\u00a0"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)91803-9"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1039\/p19750000682"},{"key":"e_1_2_6_16_1","unstructured":"Aldgarose was first described in:"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)99693-5"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1111\/j.1432-1033.1970.tb00283.x"},{"key":"e_1_2_6_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar00072a006"},{"key":"e_1_2_6_20_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_6_20_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_6_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo1003746"},{"key":"e_1_2_6_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00347a053"},{"key":"e_1_2_6_23_1","unstructured":"The analogous reaction of vinylmagnesium bromide with unprotected6gave a 1:1 mixture of isomers."},{"key":"e_1_2_6_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/jr9570001958"},{"key":"e_1_2_6_25_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)86585-0"},{"key":"e_1_2_6_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00102a047"},{"key":"e_1_2_6_27_1","unstructured":"Traces of the regioisomer with the \u201cendocyclic\u201d carbonate were also formed but could be removed during flash chromatographic purification; see also ref.\u2005[7]."},{"key":"e_1_2_6_28_1","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(88)85296-1"},{"key":"e_1_2_6_29_1","unstructured":"\u00a0"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(88)85294-8"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(88)85295-X"},{"key":"e_1_2_6_32_1","unstructured":"\u00a0"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198602121"},{"key":"e_1_2_6_33_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19860980305"},{"key":"e_1_2_6_34_2","first-page":"283","volume-title":"Preparative Carbohydrate Chemistry","author":"Schmidt R. 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