{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T05:10:50Z","timestamp":1791263450892,"version":"4.1.0"},"reference-count":62,"publisher":"Wiley","issue":"5","license":[{"start":{"date-parts":[[2007,11,22]],"date-time":"2007-11-22T00:00:00Z","timestamp":1195689600000},"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":[[2008,2,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Chemo\u2010 and stereoselective transformations of 3\u2010hydroxy\u20101,5\u2010allenynes <jats:bold>1<\/jats:bold> into a variety of new and potentially useful cyclic compounds have been achieved. Substrates bearing a silyl group at the alkyne moiety undergo purely thermal or Lewis acid catalyzed Alder\u2010ene type transformations into 2\u2010methylene\u20103\u2010vinylcyclopent\u20103\u2010enol derivatives <jats:bold>2<\/jats:bold>. When heated in the presence of a catalytic amount of PtCl<jats:sub>2<\/jats:sub> or PtCl<jats:sub>4<\/jats:sub>, these incipient cyclopentenols could be further transformed into 3\u2010vinylcyclopent\u20102\u2010enones <jats:bold>3<\/jats:bold>. On the other hand, alkyl\u2010substituted 3\u2010hydroxy\u20101,5\u2010allenynes proved to be stable under refluxing conditions. Nevertheless, PtCl<jats:sub>2<\/jats:sub> and PtCl<jats:sub>4<\/jats:sub> could selectively activate the alkyne moiety of these substrates toward intramolecular nucleophilic attack of the internal allene double bond to yield unprecedented 6\u2010methylenebicyclo[3.1.0]hexan\u20103\u2010one derivatives <jats:bold>4<\/jats:bold>. With gold\u2010based catalysts, provided that the reaction is carried out in dichloromethane, both Au<jats:sup>I<\/jats:sup> and Au<jats:sup>III<\/jats:sup> complexes selectively activate the allene fragment of the substrates toward intramolecular nucleophilic attack of the hydroxyl group to yield 2\u2010ethynyl\u20103,6\u2010dihydro\u20102<jats:italic>H<\/jats:italic>\u2010pyrans <jats:bold>5<\/jats:bold>. Compounds of type <jats:bold>4<\/jats:bold> can also be formed with Au<jats:sup>I<\/jats:sup> and Au<jats:sup>III<\/jats:sup> complexes if the reaction is carried out in toluene. The reactivity of these new compounds has been partially investigated, and polycyclic ketones were obtained after oxidation under mild conditions or gold\u2010catalyzed cycloisomerization.<\/jats:p>","DOI":"10.1002\/chem.200701522","type":"journal-article","created":{"date-parts":[[2007,11,22]],"date-time":"2007-11-22T09:47:53Z","timestamp":1195724873000},"page":"1482-1491","source":"Crossref","is-referenced-by-count":121,"title":["Alkyne versus Allene Activation in Platinum\u2010 and Gold\u2010Catalyzed Cycloisomerization of Hydroxylated 1,5\u2010Allenynes"],"prefix":"10.1002","volume":"14","author":[{"given":"Riadh","family":"Zriba","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Vincent","family":"Gandon","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Corinne","family":"Aubert","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Louis","family":"Fensterbank","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Max","family":"Malacria","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2008,2]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For recent reviews see:"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr000436x"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature05592"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200604335"},{"key":"e_1_2_6_4_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200604335"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/B615335F"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/B612008C"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200603954"},{"key":"e_1_2_6_7_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200603954"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200600368"},{"key":"e_1_2_6_9_2","first-page":"299","volume-title":"Comprehensive Organometallic Chemistry, Vol.\u200510","author":"Malacria M."},{"key":"e_1_2_6_10_2","unstructured":"For examples see:"},{"key":"e_1_2_6_11_2","first-page":"2037","author":"Blaszykowski C.","year":"2007","journal-title":"Synthesis"},{"key":"e_1_2_6_12_2","first-page":"12","author":"Nieto\u2010Oberhuber C.","year":"2006","journal-title":"Chem. Eur. J."},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja051110e"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200353207"},{"key":"e_1_2_6_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200353207"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja048094q"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja046248w"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0109343"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200501299"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200504543"},{"key":"e_1_2_6_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200504543"},{"key":"e_1_2_6_20_2","unstructured":"For gold\u2010 platinum\u2010 and gallium\u2010catalyzed cycloisomerization of 1 6\u2010allenynes see:"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo071247i"},{"key":"e_1_2_6_22_2","first-page":"575","author":"Matsuda T.","year":"2006","journal-title":"Synlett"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/hlca.200690165"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo061318y"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja031892g"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200602189"},{"key":"e_1_2_6_26_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200602189"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol062842u"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja027588p"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200501413"},{"key":"e_1_2_6_29_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200501413"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol051115g"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1039\/b508306k"},{"key":"e_1_2_6_32_2","unstructured":"We thank Prof.\u2005F.\u2005D. Toste UC\u2010Berkeley for sharing with us some findings on that topic."},{"key":"e_1_2_6_33_2","unstructured":"These compounds undergo thermal and molybdenum\u2010 or palladium\u2010catalyzed [2+2] cycloadditions to give bicyclo[3.2.0]hepta\u20101 5\u2010dienes; for examples see:"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-2005-871958"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(98)01573-1"},{"key":"e_1_2_6_36_2","unstructured":"\u00a0"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01040a034"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-0690(200001)2000:2<275::AID-EJOC275>3.0.CO;2-R"},{"key":"e_1_2_6_39_2","author":"in M. A. Brook","year":"2000","journal-title":"Silicon in Organic, Organometallic, and Polymer Chemistry"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00459a030"},{"key":"e_1_2_6_41_2","unstructured":"It is noteworthy that althoughgem\u2010dimethyl substitution in the tether improves the yield it is not a necessary feature for such cycloisomerizations. Indeed the reaction of an allenyne similar to1\u2009kwithout substituents at C4 led to the corresponding cyclopentenone in 50\u2009% yield of isolated product under the same experimental conditions."},{"key":"e_1_2_6_42_2","unstructured":"CCDC\u2010662257 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre viawww.ccdc.cam.ac.uk\/data_request\/cif."},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja074536x"},{"key":"e_1_2_6_44_2","unstructured":"\u00a0"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol061669z"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200600438"},{"key":"e_1_2_6_47_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol0481838"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol070793v"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja981183g"},{"key":"e_1_2_6_50_2","unstructured":"Protecting the hydroxyl group as an acetate led only to Alder\u2010ene cycloisomerization products with or without catalyst. Interestingly no acetate migration was observed (see ref.\u2005[1])."},{"key":"e_1_2_6_51_2","unstructured":"The reason for this chemoselectivity is not well understood at this time."},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00412a025"},{"key":"e_1_2_6_53_2","unstructured":"CCDC\u2010662258 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre viawww.ccdc.cam.ac.uk\/data_request\/cif."},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol0614830"},{"key":"e_1_2_6_55_2","unstructured":"We found that reaction of compounds4with SmI2gave a mixture of iodine\u2010containing compounds7and reduction products9. The NMR data of these products are identical to those obtained with NIS for7and by gold\u2010catalyzed cycloisomerization for9. Therefore we believe that compounds of type9display the same stereochemical arrangement as compounds7."},{"key":"e_1_2_6_56_2","unstructured":"Although the proposed stereochemistry of compounds10seems likely it was not established by NOE experiments."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200701522","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200701522","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T12:52:39Z","timestamp":1760273559000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200701522"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2008,2]]},"references-count":62,"journal-issue":{"issue":"5","published-print":{"date-parts":[[2008,2,8]]}},"alternative-id":["10.1002\/chem.200701522"],"URL":"https:\/\/doi.org\/10.1002\/chem.200701522","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2008,2]]}}}