{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,8]],"date-time":"2025-10-08T22:22:13Z","timestamp":1759962133793},"reference-count":119,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2014,7,22]],"date-time":"2014-07-22T00:00:00Z","timestamp":1405987200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["The Chemical Record"],"published-print":{"date-parts":[[2014,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>During this decade, the enantio\u2010 and stereoselective synthesis of natural products has been actively explored in the author's laboratory. In this account, the author outlines practical syntheses of the polycyclic substructures of two novel structurally formidable antibiotics, namely, the <jats:italic>trans<\/jats:italic>\u2010fused octahydronaphthalene moiety of versipelostatins and the <jats:styled-content style=\"fixed-case\">A<\/jats:styled-content>\/<jats:styled-content style=\"fixed-case\">B<\/jats:styled-content>\/<jats:styled-content style=\"fixed-case\">C<\/jats:styled-content>\u2010tricyclic decahydrofluorene moiety of GKK1032s. Both syntheses have been achieved with remarkable regio\u2010 and stereoselectivity via intramolecular <jats:styled-content style=\"fixed-case\">D<\/jats:styled-content>iels\u2013<jats:styled-content style=\"fixed-case\">A<\/jats:styled-content>lder reactions using well\u2010designed enantiomeric substrates.<\/jats:p>","DOI":"10.1002\/tcr.201402008","type":"journal-article","created":{"date-parts":[[2014,7,22]],"date-time":"2014-07-22T10:13:12Z","timestamp":1406023992000},"page":"623-640","update-policy":"http:\/\/dx.doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Our Recent Progress on the Intramolecular <scp>D<\/scp>iels\u2013<scp>A<\/scp>lder Reaction Approach in Natural Products Synthesis: Synthetic Studies of the Octahydronaphthalene Substructure of Versipelostatins and the <scp>A<\/scp>\/<scp>B<\/scp>\/<scp>C<\/scp>\u2010Tricyclic Substructure of <scp>GKK<\/scp>1032s"],"prefix":"10.1002","volume":"14","author":[{"given":"Kin\u2010Ichi","family":"Tadano","sequence":"first","affiliation":[{"name":"Department of Applied Chemistry Keio University  Hiyoshi, Kohoku\u2010ku Yokohama 223\u20108522 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2014,7,22]]},"reference":[{"key":"e_1_2_6_2_1","unstructured":"Representative reviews published since2002:"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020517)41:10<1668::AID-ANIE1668>3.0.CO;2-Z"},{"key":"e_1_2_6_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200200534"},{"key":"e_1_2_6_2_4","doi-asserted-by":"publisher","DOI":"10.1039\/B305068H"},{"key":"e_1_2_6_3_1","unstructured":"Representative reviews published since2001:"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010302)40:5<820::AID-ANIE820>3.0.CO;2-F"},{"key":"e_1_2_6_3_3","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)00121-1"},{"key":"e_1_2_6_3_4","doi-asserted-by":"publisher","DOI":"10.5059\/yukigoseikyokaishi.60.679"},{"key":"e_1_2_6_3_5","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2004.05.011"},{"key":"e_1_2_6_3_6","doi-asserted-by":"publisher","DOI":"10.1351\/pac200476111933"},{"key":"e_1_2_6_3_7","doi-asserted-by":"publisher","DOI":"10.1351\/pac200476111967"},{"key":"e_1_2_6_3_8","first-page":"141","volume":"65","author":"Heintzelman G. 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By heating under reflux in a toluene solution for twelve days the IMDA products4were obtained in a less satisfactory yield of 36%. Two Lewis acids BF3\u25cfEt2O and MeAlCl2 both in CH2Cl2at \u201378\u00b0C did not work as promoters of the IMDA reaction. Substrate5was recovered in the case of the former and decomposition of5was observed for the latter."},{"key":"e_1_2_6_27_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)96302-0"},{"key":"e_1_2_6_28_1","author":"Koizumi F.","year":"2001","journal-title":"Jpn. Kokai Tokkyo Koho"},{"key":"e_1_2_6_28_2","first-page":"209979","volume":"135","year":"2001","journal-title":"Chem. Abstr."},{"key":"e_1_2_6_28_3","first-page":"467","volume-title":"The 43rd Symposium on the Chemistry of Natural Products\u2014Symposium Papers","author":"Hasegawa A.","year":"2001"},{"key":"e_1_2_6_29_1","author":"Omura S.","year":"2002","journal-title":"Jpn. 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Unfortunately none of the diastereomeric mixtures of the corresponding acetals could be separated in diastereomerically pure forms by chromatography on silica gel."},{"key":"e_1_2_6_53_1","unstructured":"We also explored the kinetic acetylation of racemic36using lipase PS or lipase AK in the presence of vinyl acetate (40\u201360\u00b0C 110\u2013120\u2009h). However these conditions provided the correspondingO\u2010acetyl derivative in pooree. Furthermore unreacted36was recovered in less satisfactory yield and proved to be of lowee."},{"key":"e_1_2_6_54_1","unstructured":"When the acetylation of racemic36was conducted with acetic anhydride in pyridine at \u221218\u00b0C the acetate in which the angular methyl and theO\u2010acetyl group are in acisrelationship was obtained in a 79% yield along with a 21% yield of43. The structure of racemic43was confirmed based on1H NMR analysis including NOE experiments in which signal enhancement (4.4%) was observed between the hydrogen at theO\u2010acetylated acetal carbon and the angular methyl group."},{"key":"e_1_2_6_55_1","unstructured":"The enantiomeric excesses of (+)\u201036and (+)\u201044were determined by chiral HPLC analysis of 1 2\u2010di(benzoyloxy)methyl\u20101 3 5\u2010trimethylcyclohexanes which in turn were prepared from (+)\u201036or (+)\u201044as follows: 1) NaBH4 MeOH; 2) 1\u2009M HCl 0\u00b0C (for \u03b3\u2010lactone formation); 3) LiAlH4 Et2O (for diol formation); 4) BzCl pyr."},{"key":"e_1_2_6_56_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)80205-7"},{"key":"e_1_2_6_57_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01510a053"},{"key":"e_1_2_6_58_1","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(95)01049-1"},{"key":"e_1_2_6_59_1","doi-asserted-by":"publisher","DOI":"10.1002\/1099-0690(200102)2001:3<493::AID-EJOC493>3.0.CO;2-B"},{"key":"e_1_2_6_60_1","unstructured":"For the use of enantioenriched53in natural product synthesis see:"},{"key":"e_1_2_6_60_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol052917e"},{"key":"e_1_2_6_60_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200604053"},{"key":"e_1_2_6_60_4","doi-asserted-by":"publisher","DOI":"10.1021\/jo062089i"},{"key":"e_1_2_6_61_1","unstructured":"An iodide derivative similar to57 with MOM in place of TBS did not react with any metal enolate (Li Na or K) of isopropyl propionate. On the other hand iodide57reacted quantitatively with the sodium enolate of methyl diethylmalonate. After deprotection of the TBS group in the resulting alkylation product de(ethoxy)\u2010carbonylation under thermal conditions was performed. As a result a right\u2010hand \u03b1\u2010branched propionate derivative was obtained. After functionalization of the left\u2010hand terminus of this intermediate to the (E)\u2010 or (Z)\u2010unsaturated ester these substrates (MeCHCO2Et in place of CH(Me)CN in60) were subjected to base\u2010mediated intramolecular 1 4\u2010additions. Unfortunately we could not find any effective conditions for this purpose. In many cases unreacted substrate was recovered or decomposition occurred."},{"key":"e_1_2_6_62_1","unstructured":"In the NOE experiments of61 remarkable signal enhancements were observed between CH2COOEt and the CH3at C1 and also between CH2COOEt and the H at C3. In the chair\u2010like transition state in the intramolecular cyclization of60 the unsaturated ester moiety and two methyl substituents at C3 and C5 are favorably oriented equatorially and the more bulky nitrile group is also likely to direct equatorially. This transition state seems to be the most sterically favorable one and leads preferentially to the adduct61."},{"key":"e_1_2_6_63_1","first-page":"13","volume":"23","author":"Griffith W. P.","year":"1990","journal-title":"Aldrichimica Acta"},{"key":"e_1_2_6_64_1","unstructured":"We examined the IMDA reaction of82in the presence of Lewis acids. In the case of EtAlCl2(CH2Cl2 \u221278\u00b0C) the ene product85was obtained as a major product (ca. 45%). Additionally in the case of Me2AlCl (CH2Cl2 \u221278\u00b0C to ambient temperature) substantial decomposition of the substrate82was observed. Thus the yield of84could not be improved."},{"key":"e_1_2_6_65_1","unstructured":"The stereochemistry ofendo\u2010adduct86 as depicted was confirmed by extensive1H NMR analysis including NOE experiments. The Katoh\/Inoue group reported the synthesis of an A\/B\/C\u2010tricyclic compound closely related to our A\/B\/C\u2010ring equivalent86.[35c]The A\u2010ring of their compound as the enantiomer of ours possessed a methyl ester instead of our ethyl ester in86. The1H and13C NMR of these two A\/B\/C\u2010ring core structures were the same although those for86included the additional methylene signal of the ethyl ester."},{"key":"e_1_2_6_66_1","unstructured":""},{"key":"e_1_2_6_67_1","unstructured":"For some examples of the silica\u2010gel\u2010accelerated Diels\u2013Alder reaction see:"},{"key":"e_1_2_6_67_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)80045-3"},{"key":"e_1_2_6_67_3","doi-asserted-by":"publisher","DOI":"10.1021\/jo00067a027"},{"key":"e_1_2_6_67_4","doi-asserted-by":"publisher","DOI":"10.1021\/ja00057a074"},{"key":"e_1_2_6_67_5","doi-asserted-by":"publisher","DOI":"10.1021\/cr8003955"}],"container-title":["The Chemical Record"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Ftcr.201402008","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/tcr.201402008","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,11]],"date-time":"2023-09-11T20:12:35Z","timestamp":1694463155000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/tcr.201402008"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2014,7,22]]},"references-count":119,"journal-issue":{"issue":"4","published-print":{"date-parts":[[2014,8]]}},"alternative-id":["10.1002\/tcr.201402008"],"URL":"https:\/\/doi.org\/10.1002\/tcr.201402008","archive":["Portico"],"relation":{},"ISSN":["1527-8999","1528-0691"],"issn-type":[{"value":"1527-8999","type":"print"},{"value":"1528-0691","type":"electronic"}],"subject":[],"published":{"date-parts":[[2014,7,22]]},"assertion":[{"value":"2014-02-26","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2014-07-22","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}