{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,29]],"date-time":"2026-04-29T02:24:12Z","timestamp":1777429452596,"version":"3.51.4"},"reference-count":86,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2015,12,7]],"date-time":"2015-12-07T00:00:00Z","timestamp":1449446400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Eur J Org Chem"],"published-print":{"date-parts":[[2016,1]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The conformationally mobile tetramethoxy\u2010dihomooxacalix[4]arene <jats:bold>1c<\/jats:bold> is able to interact with linear and branched alkylammonium guests through an induced\u2010fit process mainly driven by H\u2010bonds and cation\u2013\u03c0 interactions. Although free <jats:bold>1c<\/jats:bold> adopts a 1,4\u2010alternate conformation in solution, in the presence of linear <jats:italic>n<\/jats:italic>BuNH<jats:sub>3<\/jats:sub><jats:sup>+<\/jats:sup> and branched <jats:italic>s<\/jats:italic>BuNH<jats:sub>3<\/jats:sub><jats:sup>+<\/jats:sup> and <jats:italic>i<\/jats:italic>PrNH<jats:sub>3<\/jats:sub><jats:sup>+<\/jats:sup> guests, it preferentially forms <jats:italic>endo<\/jats:italic>\u2010complexes in a cone conformation through adaptive structural change in response to the presence of the ammonium guests. In accordance with previous results, the DFT\u2010optimized structures of the complexes indicate that they are mainly stabilized by H\u2010bonding interactions between the guest ammonium group and the host CH<jats:sub>2<\/jats:sub>OCH<jats:sub>2<\/jats:sub> ethereal bridge.<\/jats:p>","DOI":"10.1002\/ejoc.201501319","type":"journal-article","created":{"date-parts":[[2015,12,8]],"date-time":"2015-12-08T13:15:16Z","timestamp":1449580516000},"page":"158-167","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":37,"title":["Alkylammonium Guest Induced\u2010Fit Recognition by a Flexible Dihomo\u00adoxacalix[4]arene Derivative"],"prefix":"10.1002","volume":"2016","author":[{"given":"Carmen","family":"Talotta","sequence":"first","affiliation":[]},{"given":"Carmine","family":"Gaeta","sequence":"additional","affiliation":[]},{"given":"Margherita","family":"De Rosa","sequence":"additional","affiliation":[]},{"given":"Jos\u00e9 R.","family":"Ascenso","sequence":"additional","affiliation":[]},{"given":"Paula M.","family":"Marcos","sequence":"additional","affiliation":[]},{"given":"Placido","family":"Neri","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2015,12,7]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature07768"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0896-6273(04)00115-1"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja3011379"},{"key":"e_1_2_6_5_2","volume-title":"An Introduction to Hydrogen Bonding","author":"Jefferey G. A.","year":"1997"},{"key":"e_1_2_6_6_2","unstructured":"\u00a0"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar300265y"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9603744"},{"key":"e_1_2_6_9_2","unstructured":"For further examples see:"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/cn3000586"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/cb300246j"},{"key":"e_1_2_6_12_2","unstructured":"For a comprehensive review on calixarene macrocycles see:"},{"key":"e_1_2_6_13_2","volume-title":"Calixarenes, An Introduction","author":"Gutsche C. D.","year":"2008"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19980202)37:1\/2<112::AID-ANIE112>3.0.CO;2-O"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo9615108"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201104357"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo301730m"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0811663106"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol100578z"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol200753c"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol2005159"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol3011997"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo3019945"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201102179"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol303142c"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201301570"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol4026974"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1080\/10610278.2013.872248"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4CC04668D"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo500422u"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.5b00115"},{"key":"e_1_2_6_32_2","unstructured":"\u00a0"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja711260m"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201300079"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1039\/C3RA46505E"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol301757q"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4CC03170A"},{"key":"e_1_2_6_38_2","doi-asserted-by":"crossref","DOI":"10.1039\/9781788010917","volume-title":"Crown Ethers and Cryptands: Monographs in Supramolecular Chemistry","author":"Gokel G. W.","year":"1991"},{"key":"e_1_2_6_39_2","unstructured":"\u00a0"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200460675"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja404797y"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200900305"},{"key":"e_1_2_6_43_2","first-page":"4440","volume":"51","author":"Mock W.","year":"1986","journal-title":"J. Am. Chem. Soc."},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4SC02422B"},{"key":"e_1_2_6_45_2","unstructured":"\u00a0"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo051922t"},{"key":"e_1_2_6_47_2","volume-title":"Calixarenes 2001","author":"Masci B.","year":"2001"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3765(19981002)4:10<2018::AID-CHEM2018>3.0.CO;2-I"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(97)00753-9"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1080\/10610279808034978"},{"key":"e_1_2_6_51_2","unstructured":"\u00a0"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00019a005"},{"key":"e_1_2_6_53_2","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.57.2600"},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol301757q"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja906061v"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0651355"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1039\/C005424K"},{"key":"e_1_2_6_58_2","unstructured":"\u00a0"},{"key":"e_1_2_6_59_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.1993.205"},{"key":"e_1_2_6_60_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja500376x"},{"key":"e_1_2_6_61_2","doi-asserted-by":"publisher","DOI":"10.1039\/c4ob00304g"},{"key":"e_1_2_6_62_2","doi-asserted-by":"publisher","DOI":"10.1080\/10610278.2010.500731"},{"key":"e_1_2_6_63_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2008.11.016"},{"key":"e_1_2_6_64_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200901722"},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200503906"},{"key":"e_1_2_6_66_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200290023"},{"key":"e_1_2_6_67_2","unstructured":"M. J. Frisch G. W. Trucks H. B. Schlegel G. E. Scuseria M. A. Robb J. R. Cheeseman G. Scalmani V. Barone B. Mennucci G. A. Petersson H. Nakatsuji M. Caricato X. Li H. P. Hratchian A. F. Izmaylov J. Bloino G. Zheng J. L. Sonnenberg M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai T. Vreven J. A. Montgomery Jr. J. E. Peralta F. Ogliaro M. Bearpark J. J. Heyd E. Brothers K. N. Kudin V. N. Staroverov R. Kobayashi J. Normand K. Raghavachari A. Rendell J. C. Burant S. S. Iyengar J. Tomasi M. Cossi N. Rega J. M. Millam M. Klene J. E. Knox J. B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R. E. Stratmann O. Yazyev A. J. Austin R. Cammi C. Pomelli J. W. Ochterski R. L. Martin K. Morokuma V. G. Zakrzewski G. A. Voth P. Salvador J. J. Dannenberg S. Dapprich A. D. Daniels \u00d6. Farkas J. B. Foresman J. V. Ortiz J. Cioslowski D. J. Fox Gaussian 09 revision D.01 Gaussian Inc. Wallingford CT 2009."},{"key":"e_1_2_6_68_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.475428"},{"key":"e_1_2_6_69_2","unstructured":"Usually the \u0394\u03b41H and the13C chemical shifts of the ArCH2Ar bridges of the calixarene are considered as significant to probe the conformation adopted by the macrocycle in solution based on two simple rules: the Gutsche's \u201c1H NMR \u0394\u03b4\u201d rule and the de Mendoza's \u201csingle13C NMR\u201d rule.[15a\u2013d]The first is based on the chemical shift separation of ArCH2Ar protons which may give rise to an AX AB or A2system indicative of a cone out or 1 3\u2010alternate conformation respectively. The second de Mendoza's rule is related to the13C NMR chemical shift of the ArCH2Ar group (\u03b4= 30\u201333 cone;\u03b4= 33\u201336 out; or\u03b4= 36\u201339 1 3\u2010alternate). For examples see:"},{"key":"e_1_2_6_70_2","volume-title":"Calixarenes","author":"Gutsche C. D.","year":"1989"},{"key":"e_1_2_6_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00037a037"},{"key":"e_1_2_6_72_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol052166g"},{"key":"e_1_2_6_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo401206j"},{"key":"e_1_2_6_74_2","unstructured":"\u00a0"},{"key":"e_1_2_6_75_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo981117x"},{"key":"e_1_2_6_76_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja202254x"},{"key":"e_1_2_6_77_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol0170962"},{"key":"e_1_2_6_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo900408d"},{"key":"e_1_2_6_79_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.540110405"},{"key":"e_1_2_6_80_2","unstructured":"For comparison under similar conditions the complexation ofnBuNH3+\u00b7TFPB\u2013by a conformationally fixed cone tetrapropxy\u2010p\u2010tert\u2010butylcalix[4]arene gave a similarKassvalue of 2.7\u2009\u00d7\u2009105M\u20131.[5r]This similarity is the result of two opposing effects namely the higher host preorganization and the lower number of H\u2010bonds in the calix[4]arene complex with respect to2a+\u22821ccone."},{"key":"e_1_2_6_81_2","unstructured":"The stability difference between2a+\u22821cconeand2a+\u22821c1 4\u2010altcomplexes can be mainly attributed to a more favorable complexation enthalpy for the cone complex because the entropy term is usually less relevant for such kinds of host\u2010guest complexation. In accordance with these expectations DFT calculations at the MPW1PW9[14]\/6\u201031G(d) level of theory indicated a difference in binding enthalpy (\u0394\u0394H) 29\u2010times higher with respect to the difference in entropic term [\u0394(T\u0394S)] (see Table S1) which confirms the enthalpy dominance for the complexation process."},{"key":"e_1_2_6_82_2","unstructured":"For reports on the transfer of chirality between chiral guest to achiral host see:"},{"key":"e_1_2_6_83_2","doi-asserted-by":"publisher","DOI":"10.1002\/chir.21001"},{"key":"e_1_2_6_84_2","doi-asserted-by":"publisher","DOI":"10.1039\/b909582a"},{"key":"e_1_2_6_85_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja903371d"},{"key":"e_1_2_6_86_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja906810b"}],"container-title":["European Journal of Organic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fejoc.201501319","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/ejoc.201501319","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,15]],"date-time":"2025-10-15T09:29:37Z","timestamp":1760520577000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/ejoc.201501319"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2015,12,7]]},"references-count":86,"journal-issue":{"issue":"1","published-print":{"date-parts":[[2016,1]]}},"alternative-id":["10.1002\/ejoc.201501319"],"URL":"https:\/\/doi.org\/10.1002\/ejoc.201501319","archive":["Portico"],"relation":{},"ISSN":["1434-193X","1099-0690"],"issn-type":[{"value":"1434-193X","type":"print"},{"value":"1099-0690","type":"electronic"}],"subject":[],"published":{"date-parts":[[2015,12,7]]},"assertion":[{"value":"2015-10-14","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2015-12-07","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}