{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T08:29:56Z","timestamp":1790756996478,"version":"4.1.0"},"reference-count":93,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2002,12,30]],"date-time":"2002-12-30T00:00:00Z","timestamp":1041206400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2003,1,3]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The completion of the first total synthesis of the complex resin glycoside woodrosin I (<jats:bold>1<\/jats:bold>) is outlined using the building blocks described in the preceding paper. Key steps involve the TMSOTf\u2010catalyzed coupling of diol <jats:bold>2<\/jats:bold> with trichloroacetimidate <jats:bold>3<\/jats:bold> which leads to the selective formation of orthoester <jats:bold>5<\/jats:bold> rather than to the expected tetrasaccharide. Diene <jats:bold>5<\/jats:bold>, on treatment with catalytic amounts of the Grubbs carbene complex <jats:bold>6<\/jats:bold> or the phenylindenylidene ruthenium complex <jats:bold>7<\/jats:bold>, undergoes a high yielding ring closing olefin metathesis reaction (RCM) to afford macrolide <jats:bold>8<\/jats:bold>. Exposure of the latter to the rhamnosyl donor <jats:bold>4<\/jats:bold> in the presence of TMSOTf under \u201cinverse glycosylation\u201d conditions delivers compound <jats:bold>9<\/jats:bold> by a process involving glycosylation of the sterically hindered 2\u2032\u2010OH group and concomitant rearrangement of the adjacent orthoester into the desired <jats:italic>\u03b2<\/jats:italic>\u2010glycoside. This transformation constitutes one of the most advanced applications of the Kochetkov glycosidation method reported to date. Cleavage of the chloroacetate followed by exhaustive hydrogenation completes the total synthesis of the targeted glycolipid <jats:bold>1<\/jats:bold>.<\/jats:p>","DOI":"10.1002\/chem.200390026","type":"journal-article","created":{"date-parts":[[2002,12,30]],"date-time":"2002-12-30T19:59:54Z","timestamp":1041278394000},"page":"320-326","source":"Crossref","is-referenced-by-count":72,"title":["Total Synthesis of Woodrosin I\u2014Part 2: Final Stages Involving RCM and an Orthoester Rearrangement"],"prefix":"10.1002","volume":"9","author":[{"given":"Alois","family":"F\u00fcrstner","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fabien","family":"Jeanjean","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Patrick","family":"Razon","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Conny","family":"Wirtz","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Richard","family":"Mynott","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2002,12,30]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1248\/cpb.41.1925"},{"key":"e_1_2_6_2_2","unstructured":"The expression \u201cwoodrosin\u201d derives from the trivial name ofIpomoea tuberosawhich is commonly called \u201cwoodrose\u201d after the shape of its dried calyx."},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19951072220"},{"key":"e_1_2_6_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199525201"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo960655b"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo971413u"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19971092118"},{"key":"e_1_2_6_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199723441"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo9711450"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja991361l"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo971918k"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1524\/zkri.2000.215.2.114"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo0012952"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.4052\/tigg.13.1"},{"key":"e_1_2_6_13_2","unstructured":"Reviews:"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19860980305"},{"key":"e_1_2_6_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198602121"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0065-2318(08)60150-X"},{"key":"e_1_2_6_16_2","first-page":"283","volume-title":"Preparative Carbohydrate Chemistry","author":"Schmidt R. 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Engl."},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1023\/A:1019117012154"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1039\/a703881j"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200390025"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20020617)114:12<2203::AID-ANGE2203>3.0.CO;2-M"},{"key":"e_1_2_6_25_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020617)41:12<2097::AID-ANIE2097>3.0.CO;2-T"},{"key":"e_1_2_6_26_2","unstructured":"Rigorous exclusion of moisture and constant monitoring of the reaction by TLC are crucial due to the lability of the benzylidene acetal protecting group in substrate2and the emerging product5under these Lewis acidic conditions."},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/jlac.1990199001204"},{"key":"e_1_2_6_28_2","unstructured":"Esters other than chloroacetates at O\u20102 of various glycosyl donors may similarly lead to orthoesters in particular in attempted glycosylations with sterically hindered secondary alcohols. This bias is generally increased if the reaction medium is buffered with bases. For examples and a pertinent discussion of the relevant reaction parameters see the following publications and references therein:"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja971640d"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1139\/v79-335"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1002\/jlac.198219820105"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1002\/jlac.198619860411"},{"key":"e_1_2_6_33_2","unstructured":"For orthoester to glycoside rearrangements see for example:"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(64)80013-7"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(67)85014-2"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0008-6215(00)86094-2"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00020a006"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0108503"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo960733v"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1997-4472"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1007\/3-540-69708-X_2"},{"key":"e_1_2_6_42_2","unstructured":"Applications:"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9719945"},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(99)00302-6"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo982088t"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo0009999"},{"key":"e_1_2_6_47_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol0069554"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(96)01590-0"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1997-930"},{"key":"e_1_2_6_50_2","unstructured":"\u00a0"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19951071818"},{"key":"e_1_2_6_51_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199520391"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja952676d"},{"key":"e_1_2_6_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00074a086"},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20011119)7:22<4811::AID-CHEM4811>3.0.CO;2-P"},{"key":"e_1_2_6_55_2","unstructured":"For previous applications of this catalyst see:"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1039\/a900187e"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo991021i"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo991611g"},{"key":"e_1_2_6_59_2","doi-asserted-by":"publisher","DOI":"10.1002\/1439-7633(20010105)2:1<60::AID-CBIC60>3.0.CO;2-P"},{"key":"e_1_2_6_60_2","doi-asserted-by":"publisher","DOI":"10.1039\/b101148k"},{"key":"e_1_2_6_61_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)92704-7"},{"key":"e_1_2_6_62_2","volume":"93","author":"Ogawa T.","year":"1981","journal-title":"Carbohydr. 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