{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,11]],"date-time":"2026-06-11T22:59:11Z","timestamp":1781218751666,"version":"3.54.1"},"reference-count":140,"publisher":"Wiley","issue":"51","license":[{"start":{"date-parts":[[2015,11,10]],"date-time":"2015-11-10T00:00:00Z","timestamp":1447113600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"name":"DFG"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2015,12,14]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Natural products of polyketide origin with a high level of symmetry, in particular <jats:italic>C<\/jats:italic><jats:sub>2<\/jats:sub>\u2010symmetric diolides as a special macrolactone\u2010based product class, often possess a broad spectrum of biological activity. An efficient route to this important structural motif was developed as part of a concise and highly convergent synthesis of clavosolide\u2005A. This strategy features an atom\u2010economic \u201chead\u2010to\u2010tail\u201d dimerization by the stereoselective rhodium\u2010catalyzed addition of carboxylic acids to terminal allenes with the simultaneous construction of two new stereocenters. The excellent efficiency and selectivity with which the <jats:italic>C<\/jats:italic><jats:sub>2<\/jats:sub>\u2010symmetric core structures were obtained are remarkable considering the outcome under classical dimerization conditions. Furthermore, this approach facilitates late\u2010stage modification and provides ready access to potential new lead structures.<\/jats:p>","DOI":"10.1002\/anie.201506618","type":"journal-article","created":{"date-parts":[[2015,11,10]],"date-time":"2015-11-10T12:07:41Z","timestamp":1447157261000},"page":"15530-15534","source":"Crossref","is-referenced-by-count":57,"title":["Atom\u2010Economical Dimerization Strategy by the Rhodium\u2010Catalyzed Addition of Carboxylic Acids to Allenes: Protecting\u2010Group\u2010Free Synthesis of Clavosolide\u2005A and Late\u2010Stage Modification"],"prefix":"10.1002","volume":"54","author":[{"given":"Alexander M.","family":"Haydl","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bernhard","family":"Breit","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2015,11,10]]},"reference":[{"key":"e_1_2_3_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/cbdv.201000038"},{"key":"e_1_2_3_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr040629a"},{"key":"e_1_2_3_3_2","unstructured":"\u00a0"},{"key":"e_1_2_3_4_2","doi-asserted-by":"publisher","DOI":"10.1038\/nrd2590"},{"key":"e_1_2_3_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm1012374"},{"key":"e_1_2_3_6_2","first-page":"221","volume":"49","author":"Proska B.","year":"2000","journal-title":"Ceska Slov. Farm."},{"key":"e_1_2_3_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00841a058"},{"key":"e_1_2_3_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00490a052"},{"key":"e_1_2_3_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1567-5769(01)00119-9"},{"key":"e_1_2_3_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200701065"},{"key":"e_1_2_3_10_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200701065"},{"key":"e_1_2_3_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja068053p"},{"key":"e_1_2_3_12_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1330"},{"key":"e_1_2_3_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0558948"},{"key":"e_1_2_3_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja036521e"},{"key":"e_1_2_3_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0315309"},{"key":"e_1_2_3_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00085a050"},{"key":"e_1_2_3_17_2","unstructured":"\u00a0"},{"key":"e_1_2_3_18_2","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.52.1989"},{"key":"e_1_2_3_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)96566-3"},{"key":"e_1_2_3_20_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)85585-X"},{"key":"e_1_2_3_21_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)97066-7"},{"key":"e_1_2_3_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201203035"},{"key":"e_1_2_3_22_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201203035"},{"key":"e_1_2_3_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201404408"},{"key":"e_1_2_3_23_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201404408"},{"key":"e_1_2_3_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja204228q"},{"key":"e_1_2_3_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja509973r"},{"key":"e_1_2_3_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201501922"},{"key":"e_1_2_3_26_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201501922"},{"key":"e_1_2_3_27_2","unstructured":"\u00a0"},{"key":"e_1_2_3_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201206594"},{"key":"e_1_2_3_28_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201206594"},{"key":"e_1_2_3_29_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201309126"},{"key":"e_1_2_3_29_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201309126"},{"key":"e_1_2_3_30_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201403682"},{"key":"e_1_2_3_30_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201403682"},{"key":"e_1_2_3_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja411397g"},{"key":"e_1_2_3_32_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201407935"},{"key":"e_1_2_3_32_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201407935"},{"key":"e_1_2_3_33_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201411402"},{"key":"e_1_2_3_33_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201411402"},{"key":"e_1_2_3_34_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201501758"},{"key":"e_1_2_3_34_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201501758"},{"key":"e_1_2_3_35_2","unstructured":"\u00a0"},{"key":"e_1_2_3_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9902796"},{"key":"e_1_2_3_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol702914p"},{"key":"e_1_2_3_38_2","doi-asserted-by":"publisher","DOI":"10.1039\/b900976k"},{"key":"e_1_2_3_39_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1001"},{"key":"e_1_2_3_40_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199213351"},{"key":"e_1_2_3_40_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19921041024"},{"key":"e_1_2_3_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja039774g"},{"key":"e_1_2_3_42_2","unstructured":"\u00a0"},{"key":"e_1_2_3_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja210149g"},{"key":"e_1_2_3_44_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201303300"},{"key":"e_1_2_3_45_2","unstructured":"\u00a0"},{"key":"e_1_2_3_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja1108613"},{"key":"e_1_2_3_47_2","doi-asserted-by":"publisher","DOI":"10.1039\/C2SC00812B"},{"key":"e_1_2_3_48_2","unstructured":"\u00a0"},{"key":"e_1_2_3_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9409804"},{"key":"e_1_2_3_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020027w"},{"key":"e_1_2_3_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200605113"},{"key":"e_1_2_3_51_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200605113"},{"key":"e_1_2_3_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol901031b"},{"key":"e_1_2_3_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol0343562"},{"key":"e_1_2_3_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja026337d"},{"key":"e_1_2_3_55_2","unstructured":"\u00a0"},{"key":"e_1_2_3_56_2","doi-asserted-by":"publisher","DOI":"10.1007\/128_2009_16"},{"key":"e_1_2_3_57_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja039107n"},{"key":"e_1_2_3_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja070424u"},{"key":"e_1_2_3_59_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja1030936"},{"key":"e_1_2_3_60_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201204579"},{"key":"e_1_2_3_60_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201204579"},{"key":"e_1_2_3_61_2","unstructured":"\u00a0"},{"key":"e_1_2_3_62_2","doi-asserted-by":"publisher","DOI":"10.1021\/np010495l"},{"key":"e_1_2_3_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/np020193z"},{"key":"e_1_2_3_64_2","doi-asserted-by":"publisher","DOI":"10.1021\/np9008128"},{"key":"e_1_2_3_65_2","unstructured":"For prior syntheses of the clavosolide family see:"},{"key":"e_1_2_3_66_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol0611705"},{"key":"e_1_2_3_67_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol800386d"},{"key":"e_1_2_3_68_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol052851n"},{"key":"e_1_2_3_69_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol0611752"},{"key":"e_1_2_3_70_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2008.03.039"},{"key":"e_1_2_3_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol8028302"},{"key":"e_1_2_3_72_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol302744t"},{"key":"e_1_2_3_73_2","unstructured":"For prior syntheses of cyanolide\u2005A see:"},{"key":"e_1_2_3_74_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol101022z"},{"key":"e_1_2_3_75_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo101782q"},{"key":"e_1_2_3_76_2","doi-asserted-by":"publisher","DOI":"10.1039\/C0OB00971G"},{"key":"e_1_2_3_77_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo102401v"},{"key":"e_1_2_3_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol402095g"},{"key":"e_1_2_3_79_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo201210u"},{"key":"e_1_2_3_80_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201300843"},{"key":"e_1_2_3_80_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201300843"},{"key":"e_1_2_3_81_2","unstructured":"\u00a0"},{"key":"e_1_2_3_82_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200500369"},{"key":"e_1_2_3_82_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200500369"},{"key":"e_1_2_3_83_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20000901)39:17<3012::AID-ANIE3012>3.0.CO;2-G"},{"key":"e_1_2_3_83_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20000901)112:17<3140::AID-ANGE3140>3.0.CO;2-G"},{"key":"e_1_2_3_84_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar000114f"},{"key":"e_1_2_3_85_2","unstructured":"\u00a0"},{"key":"e_1_2_3_86_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr010007e"},{"key":"e_1_2_3_87_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr0200217"},{"key":"e_1_2_3_88_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol050840o"},{"key":"e_1_2_3_89_2","unstructured":"\u00a0"},{"key":"e_1_2_3_90_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201000775"},{"key":"e_1_2_3_90_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201000775"},{"key":"e_1_2_3_91_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200904761"},{"key":"e_1_2_3_91_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200904761"},{"key":"e_1_2_3_92_2","doi-asserted-by":"publisher","DOI":"10.1002\/ijch.201100006"},{"key":"e_1_2_3_93_2","first-page":"163","author":"Wach J.\u2010Y.","year":"2012","journal-title":"Synlett"},{"key":"e_1_2_3_94_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200390327"},{"key":"e_1_2_3_94_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200390298"},{"key":"e_1_2_3_95_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00217a027"},{"key":"e_1_2_3_96_2","unstructured":"For further details see the Supporting Information."},{"key":"e_1_2_3_97_2","unstructured":"The modified Nokami crotyl\u2010transfer reagent6\u2009bis a new reagent and was prepared in three steps from commercially available (R)\u2010pulegone. For further details see the Supporting Information."},{"key":"e_1_2_3_98_2","unstructured":"\u00a0"},{"key":"e_1_2_3_99_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198007311"},{"key":"e_1_2_3_99_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19800920933"},{"key":"e_1_2_3_100_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0065-2318(08)60150-X"},{"key":"e_1_2_3_101_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00083a013"},{"key":"e_1_2_3_102_2","doi-asserted-by":"publisher","DOI":"10.1080\/07328308708058879"},{"key":"e_1_2_3_103_2","unstructured":"For further details concerning the transformation of12and14into3to confirm their relative configuration see the Supporting Information."},{"key":"e_1_2_3_104_2","unstructured":"For studies concerning C1homologation through cross\u2010metathesis with propene or (Z)\u2010butene analogues see:"},{"key":"e_1_2_3_105_2","doi-asserted-by":"publisher","DOI":"10.1039\/b105031c"},{"key":"e_1_2_3_106_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9025243"},{"key":"e_1_2_3_107_2","unstructured":"Cross\u2010metathesis with higher olefins is more common and usually gives betterE\/Zproduct ratios; see:"},{"key":"e_1_2_3_108_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200802043"},{"key":"e_1_2_3_108_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200802043"},{"key":"e_1_2_3_109_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja3076988"},{"key":"e_1_2_3_110_2","unstructured":"\u00a0"},{"key":"e_1_2_3_111_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0205232"},{"key":"e_1_2_3_112_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol026084t"},{"key":"e_1_2_3_113_2","unstructured":"The diastereoselectivity of this reaction could not be determined easily but is known to be high in transformations with related structures; see Refs.\u2005[16a b]."},{"key":"e_1_2_3_114_2","unstructured":"\u00a0"},{"key":"e_1_2_3_115_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200501798"},{"key":"e_1_2_3_115_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200501798"},{"key":"e_1_2_3_116_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0348997"},{"key":"e_1_2_3_117_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0637954"},{"key":"e_1_2_3_118_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja044280k"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201506618","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201506618","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.201506618","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201506618","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,8,29]],"date-time":"2023-08-29T11:17:33Z","timestamp":1693307853000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.201506618"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2015,11,10]]},"references-count":140,"journal-issue":{"issue":"51","published-print":{"date-parts":[[2015,12,14]]}},"alternative-id":["10.1002\/anie.201506618"],"URL":"https:\/\/doi.org\/10.1002\/anie.201506618","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2015,11,10]]}}}