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all of these however provided correct high\u2010resolution mass spectra."},{"key":"e_1_2_2_47_2","unstructured":"The reaction of monoketone14and the sodium derivative of (EtO)2P(\uf8feO)\uf8ffCH2\uf8ffCO2Et gave the ethyl ester\/Weinreb amide analogue of17as anE:Zmixture (93\u2009% yield E:Z=59:41)."},{"key":"e_1_2_2_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00408a041"},{"key":"e_1_2_2_49_2","unstructured":"Monoketone14and the sodium derivative of a commercial 90:10trans:cismixture of (EtO)2P(\uf8feO)\uf8ffCH2\uf8ffCH\uf8feCH\uf8ffCO2Et gave all four diene stereoisomers of the ethyl ester\/Weinreb amide analogue of18in a combined yield of 49\u2009%."},{"key":"e_1_2_2_50_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1981-29377"},{"key":"e_1_2_2_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo000068x"},{"key":"e_1_2_2_52_2","first-page":"2135","author":"Olpp T.","year":"2004","journal-title":"Synthesis"},{"key":"e_1_2_2_53_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1975-23921"},{"key":"e_1_2_2_54_2","doi-asserted-by":"publisher","DOI":"10.1039\/b005617k"},{"key":"e_1_2_2_55_2","doi-asserted-by":"publisher","DOI":"10.1016\/0031-9422(83)80010-7"},{"key":"e_1_2_2_56_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1993-22642"},{"key":"e_1_2_2_57_2","doi-asserted-by":"publisher","DOI":"10.1271\/bbb.64.1444"},{"key":"e_1_2_2_58_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1994-22755"},{"key":"e_1_2_2_59_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2002.1248"},{"key":"e_1_2_2_60_2","unstructured":"(trans)\u20101\u2010[(1S 2R)\u20101 2\u2010Epoxy\u20102 6 6\u2010trimethylcyclohexyl]\u20102\u2010(tributylstannyl)ethene (trans\u201031):1H NMR (500.0 MHz CDCl3):\u03b4=0.88 (t J4\u2032\u2032 3\u2032\u2032=7.3 Hz 3\u00d74\u2032\u2032\u2010H3) superimposed in part with 0.87\u20130.91 (m 3\u00d71\u2032\u2032\u2010H2) 0.93 1.09 and 1.15 [3\u00d7s 2\u2032\u2010CH3 6\u2032\u2010(CH3)2] 1.00\u20131.06 (m 5\u2032\u2010H1) 1.30 (qt J3\u2032\u2032 4\u2032\u2032=J3\u2032\u2032 2\u2032\u2032=7.3 Hz 3\u00d73\u2032\u2032\u2010H2) 1.39\u20131.53 ppm (m 4\u2032\u2010H2 5\u2032\u2010H2 3\u00d72\u2032\u2032\u2010H2) AB signal (\u03b4A=1.72 \u03b4B=1.87 2JAB=15.2 Hz additionally split byJA 4\u2032=5.7 Hz andJB 4\u2032=7.9 Hz 3\u2032\u2010H2) AB signal (\u03b4A=6.151 \u03b4B=6.166 JAB=19.2 Hz; accompanying Sn isotope satellites as 2 d per signal branch:3J=70.5 Hz 3J=67.5 Hz 2J=74.9 Hz 2J=71.7 Hz; A: 1\u2010H B: 2\u2010H)."},{"key":"e_1_2_2_61_2","unstructured":"Stannanecis\u201031was prepared as a racemic mixture from (2 6 6\u2010trimethyl\u20101\u2010cyclohexenyl)acetylene in two steps: radical\u2010mediated hydrostannylation with Bu3SnH; epoxidation withmeta\u2010chloroperbenzoic acid: F. v. d. Ohe Dissertation Universit\u00e4t Freiburg 2001."},{"key":"e_1_2_2_62_2","unstructured":"(5S)\u20103\u2010Bromo\u20105\u2010[(2trans 4E 1S)\u20101\u2010hydroxy\u20105\u2010(methoxycarbonyl)\u20102\u2010methyl\u20102 4\u2010pentadienyl]\u20102(5\u2009H)\u2010furanone (35):1H NMR (500.0 MHz CDCl3):\u03b4=1.97 (d 4J2\u2032\u2010Me 3\u2032=1.2 Hz 2\u2032\u2010CH3) 2.91 (br\u2009s OH) 3.77 (s OCH3) 4.30 (br\u2009d J1\u2032 5=5.5 Hz 1\u2032\u2010H) 5.08 (dd J5 1\u2032=5.6 Hz J5 4=1.8 Hz 5\u2010H) 5.94 (d J5\u2032 4\u2032=15.2 Hz 5\u2032\u2010H) 6.27 (dmc J3\u2032 4\u2032=11.5 Hz 3\u2032\u2010H) 7.44 (d J4 5=1.9 Hz 4\u2010H) 7.55 ppm (dd J4\u2032 5\u2032=15.4 Hz J4\u2032 3\u2032=11.5 Hz 4\u2032\u2010H)."},{"key":"e_1_2_2_63_2","first-page":"1","volume":"50","author":"Farina V.","year":"1997","journal-title":"Org. React."},{"key":"e_1_2_2_64_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00025a025"},{"key":"e_1_2_2_65_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00306a012"},{"key":"e_1_2_2_66_2","unstructured":"(5S)\u20103\u2010{(E)\u20102\u2010[(1S 2R)\u20101 2\u2010Epoxy\u20102 6 6\u2010trimethylcyclohexyl]ethenyl}\u20105\u2010[(2E 4trans 1S)\u20101\u2010hydroxy\u20105\u2010(methoxycarbonyl)\u20102\u2010methyl\u20102 4\u2010pentadienyl]\u20102(5\u2009H)\u2010furanone (5):1H NMR (500.0 MHz CDCl3):\u03b4=0.93 1.13 and 1.15 [3\u00d7s 2\u2032\u2032\u2010CH3 6\u2032\u2032\u2010(CH3)2] 1.06\u20131.10 (m 5\u2032\u2032\u2010H1) ca. 1.39\u20131.49 (m 4\u2032\u2032\u2010H1 5\u2032\u2032\u2010H2) 1.61\u20131.68 (m 4\u2032\u2032\u2010H2) AB signal (\u03b4A=1.75 \u03b4B=1.90 2JAB=15.1 Hz additionally split byJA 4\u2032\u2032\u2010H(1)=JA 4\u2032\u2032\u2010H(2)=5.2 Hz JB 4\u2032\u2032\u2010H(1)=JB 4\u2032\u2032\u2010H(2)=7.6 Hz 3\u2032\u2032\u2010H2) 1.99 (d 4J2\u2032\u2032\u2032\u2010Me 3\u2032\u2032\u2032=1.4 Hz 2\u2032\u2032\u2032\u2010CH3) 2.57 (br\u2009s OH) 3.77 (s OCH3) 4.18 (d J1\u2032\u2032\u2032 5=6.2 Hz 1\u2032\u2032\u2032\u2010H) 5.01 (mc approximately interpretable as dd J5 1\u2032\u2032\u2032=6.3 Hz J5 4=1.9 Hz 5\u2010H) 5.95 (d J5\u2032\u2032\u2032 4\u2032\u2032\u2032=15.3 Hz 5\u2032\u2032\u2032\u2010H) 6.28 (mc approximately interpretable as ddq J3\u2032\u2032\u2032 4\u2032\u2032\u2032=11.6 Hz 4J3\u2032\u2032\u2032 5\u2032\u2032\u2032\u22481.4 Hz 4J3\u2032\u2032\u2032 2\u2032\u2032\u2032\u2010Me\u22480.8 Hz 3\u2032\u2032\u2032\u2010H) 6.29 (d J1\u2032 2\u2032=15.7 Hz 1\u2032\u2010H) 6.95 (d J4 5=2.1 Hz 4\u2010H) 7.22 (d J2\u2032 1\u2032=15.6 Hz 2\u2032\u2010H) 7.57 ppm (dd J4\u2032\u2032\u2032 5\u2032\u2032\u2032=15.1 Hz J4\u2032\u2032\u2032 3\u2032\u2032\u2032=11.5 Hz 4\u2032\u2032\u2032\u2010H)."},{"key":"e_1_2_2_67_2","unstructured":"(5Z)\u20103\u2010{(E)\u20102\u2010[(1S 2R)\u20101 2\u2010Epoxy\u20102 6 6\u2010trimethylcyclohexyl]ethenyl}\u20105\u2010[(2E 4trans)\u20105\u2010(methoxycarbonyl)\u20102\u2010methyl\u20102 4\u2010pentadienylidene]\u20102(5\u2009H)\u2010furanone (37): To a solution of \u03b3\u2010(\u03b1\u2010hydroxyalkyl)butenolide5(22.4 mg 55.7 \u03bcmol) in THF (3 mL; the solvent contained 250 mg 2 6\u2010di\u2010tert\u2010butyl\u20104\u2010cresol per L and was degassed prior to use) was added DEAD (17.6 \u03bcL 19.4 mg 111 \u03bcmol 2.0 equiv) at \u221230\u2009\u00b0C under argon atmosphere and exclusion of light. After 10 min PPh3(29.2 mg 111 \u03bcmol 2.0 equiv) was added and the reaction mixture was stirred at \u221230\u2009\u00b0C for another 2 h. Two\u2010thirds of the solvent was removed under reduced pressure at \u221230\u2009\u00b0C. A small portion of chromatography eluent (1 mL) was added and this mixture was subjected to flash chromatography (cyclohexane:EtOAc 10:1 with 0.7 vol\u2009% NEt3; degassed) which rendered the product (19.2 mg 90\u2009%) as an intensely yellow solid. For selected1H NMR (500.0 MHz C6D6) data see Scheme 6."},{"key":"e_1_2_2_68_2","unstructured":"Following the suggestion of a referee we also conducted the Stille coupling of the (dienoic ester)\u2010containing bromobutenolide35and the (4S)\u20104\u2010hydroxy analogue oftrans\u201031.[30]This provided the (4S)\u20104\u2010hydroxy analogue of5 a precursor of the hydroxylated butenolide moiety of natural peridinin with unaltered yield (83\u2009%). Because of the presence of the 4\u2010hydroxy group which had to be conserved the subsequent activation of the 1\u2032\u2010hydroxy group was best carried out under modified conditions: treatment of (4S)\u20104\u2010hydroxy\u20105at \u221210\u2009\u00b0C in THF with 9 equiv each of DEAD and PPh3(71\u2009% yield). In the same way when we processed the aldehyde analogue of the ester\u2010substituted bromobutenolide35 we could swap the steps i.e. start with the elimination and couple with the (4S)\u20104\u2010hydroxy analogue oftrans\u201031. The detailed results will be reported in a full paper."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.200460259","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.200460259","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,10,16]],"date-time":"2023-10-16T13:52:17Z","timestamp":1697464337000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.200460259"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2005,2,22]]},"references-count":71,"journal-issue":{"issue":"10","published-print":{"date-parts":[[2005,2,25]]}},"alternative-id":["10.1002\/anie.200460259"],"URL":"https:\/\/doi.org\/10.1002\/anie.200460259","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2005,2,22]]}}}