{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,1]],"date-time":"2026-10-01T07:30:33Z","timestamp":1790839833682,"version":"4.1.0"},"reference-count":30,"publisher":"Wiley","issue":"33","license":[{"start":{"date-parts":[[2018,7,5]],"date-time":"2018-07-05T00:00:00Z","timestamp":1530748800000},"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":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2018,8,13]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Pairing a range of bis(aryl) zinc reagents ZnAr<jats:sub>2<\/jats:sub> with the stronger Lewis acidic [(ZnAr<jats:sup>F<\/jats:sup><jats:sub>2<\/jats:sub>)] (Ar<jats:sup>F<\/jats:sup>=C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>), enables highly stereoselective cross\u2010coupling between glycosyl bromides and ZnAr<jats:sub>2<\/jats:sub> without the use of a transition metal. Reactions occur at room temperature with excellent levels of stereoselectivity, where ZnAr<jats:sup>F<\/jats:sup><jats:sub>2<\/jats:sub> acts as a non\u2010coupling partner although its presence is crucial for the execution of the C(sp<jats:sup>2<\/jats:sup>)\u2013C(sp<jats:sup>3<\/jats:sup>) bond formation process. Mechanistic studies have uncovered a unique synergistic partnership between the two zinc reagents, which circumvents the need for transition\u2010metal catalysis or forcing reaction conditions. Key to the success of the coupling is the avoidance of solvents that act as Lewis bases versus diarylzinc compounds (e.g. THF).<\/jats:p>","DOI":"10.1002\/anie.201805758","type":"journal-article","created":{"date-parts":[[2018,6,1]],"date-time":"2018-06-01T17:24:21Z","timestamp":1527873861000},"page":"10630-10634","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Exploiting Synergistic Effects in Organozinc Chemistry for Direct Stereoselective C\u2010Glycosylation Reactions at Room Temperature"],"prefix":"10.1002","volume":"57","author":[{"given":"Alberto","family":"Hern\u00e1n\u2010G\u00f3mez","sequence":"first","affiliation":[{"name":"WestCHEM Department of Pure and Applied Chemistry University of Strathclyde  295 Cathedral Street Glasgow G1 1XL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Samantha A.","family":"Orr","sequence":"additional","affiliation":[{"name":"WestCHEM Department of Pure and Applied Chemistry University of Strathclyde  295 Cathedral Street Glasgow G1 1XL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marina","family":"Uzelac","sequence":"additional","affiliation":[{"name":"WestCHEM Department of Pure and Applied Chemistry University of Strathclyde  295 Cathedral Street Glasgow G1 1XL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alan R.","family":"Kennedy","sequence":"additional","affiliation":[{"name":"WestCHEM Department of Pure and Applied Chemistry University of Strathclyde  295 Cathedral Street Glasgow G1 1XL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Santiago","family":"Barroso","sequence":"additional","affiliation":[{"name":"Pharmaceutical Development and Manufacturing Sciences Janssen Pharmaceutica  Turnhoutseweg 30 2340 Beerse Belgium"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xavier","family":"Jusseau","sequence":"additional","affiliation":[{"name":"Pharmaceutical Development and Manufacturing Sciences Janssen Pharmaceutica  Turnhoutseweg 30 2340 Beerse Belgium"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"S\u00e9bastien","family":"Lemaire","sequence":"additional","affiliation":[{"name":"Pharmaceutical Development and Manufacturing Sciences Janssen Pharmaceutica  Turnhoutseweg 30 2340 Beerse Belgium"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Vittorio","family":"Farina","sequence":"additional","affiliation":[{"name":"Pharmaceutical Development and Manufacturing Sciences Janssen Pharmaceutica  Turnhoutseweg 30 2340 Beerse Belgium"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3998-7506","authenticated-orcid":false,"given":"Eva","family":"Hevia","sequence":"additional","affiliation":[{"name":"WestCHEM Department of Pure and Applied Chemistry University of Strathclyde  295 Cathedral Street Glasgow G1 1XL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2018,7,5]]},"reference":[{"key":"e_1_2_2_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527619535"},{"key":"e_1_2_2_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5b02718"},{"key":"e_1_2_2_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201301404"},{"key":"e_1_2_2_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201412249"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201412249"},{"key":"e_1_2_2_5_1","unstructured":"\u00a0"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol300220p"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.6b00074"},{"key":"e_1_2_2_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201411403"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201411403"},{"key":"e_1_2_2_9_1","unstructured":"For some examples see:"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1038\/nrd3180"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.bmcl.2010.11.031"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm100332n"},{"key":"e_1_2_2_13_1","unstructured":"13C\u2005NMR titration experiments allowed the calculation of the association constant (Keq) between ZnPh2and DBE to give coordination adduct [ZnPh2(DBE)] (Keq=2.33\u2009m\u22121). See Supporting Information for details. In contrast DOSY NMR studies have shown that in [D8]toluene solution ZnPh2exists as a dimer in equilibrium with its monomeric form which is coordinatively unsaturated and could be expected to exhibit higher Lewis-acid reactivity."},{"key":"e_1_2_2_14_1","unstructured":"X-ray crystallographic studies showed [ZnPh2(TMEDA)] exhibits a monomeric structure with TMEDA coordinated as a chelate to Zn. This structure is retained in toluene [D8]-solutions (See Supporting Information for details)."},{"key":"e_1_2_2_15_1","unstructured":"See Supporting Information for details."},{"key":"e_1_2_2_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200601739"},{"key":"e_1_2_2_17_1","unstructured":"Ammonium zincate complex3was obtained in a 86\u2009% isolated yield. DOSY NMR studies are consistent with the retention of its solid-state structure (Figure\u20052) in deuterated toluene."},{"key":"e_1_2_2_18_1","unstructured":"13C\u2005NMR titration studies support product inhibition by the formation of coordination adduct [ZnArF2(2\u2009a)] (Keq=25.21\u2009m\u22121). It should also be noted that DOSY NMR experiments of solutions of ZnPh2and4in [D8]toluene indicate that these two zinc compounds do not form a heteroleptic bis(aryl) [PhZnArF] complex but exist as separate entities. See Supporting Information for details."},{"key":"e_1_2_2_19_1","unstructured":"13C\u2005NMR titration studies support formation of coordination adducts [ZnArF2(1)] and [ZnArF2(DBE)] (Keq=13.53\u2009m\u22121and 3.53\u2009m\u22121respectively) see Supporting Information for details."},{"key":"e_1_2_2_20_1","unstructured":"\u00a0"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja8041564"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja068950t"},{"key":"e_1_2_2_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201204786"},{"key":"e_1_2_2_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201204786"},{"key":"e_1_2_2_24_1","unstructured":"Maximum concentration of 12.51\u2005ppb\u2009mg\u22121was observed for iron impurities. See Supporting Information for full details."},{"key":"e_1_2_2_25_1","unstructured":"This contrasts with results reported when ZnAr2(Ar=4-CF3-C6H4)2is used in the presence of LiBr which furnished the relevant coupling product in a 50\u2009% yield after 24\u2005h at 110\u2009\u00b0C. See Ref.\u2005[5a]."},{"key":"e_1_2_2_26_1","unstructured":"1H\u2005NMR studies adding variable amounts of PhZnBr to a 1:1 mixture of ZnPh2and4in [D8]toluene using ferrocene as an internal standard have shown an increase in the concentration of ZnPh2in solution consistent with the Schlenk-type equilibrium being driven towards formation of ZnPh2and ZnBr2. See Supporting Information for details."},{"key":"e_1_2_2_27_1","unstructured":"By treatingBandCas steady-state intermediates a rate law in agreement for these observations is shown in Supporting Information."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201805758","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201805758","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.201805758","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201805758","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,10]],"date-time":"2023-09-10T21:45:04Z","timestamp":1694382304000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.201805758"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,7,5]]},"references-count":30,"journal-issue":{"issue":"33","published-print":{"date-parts":[[2018,8,13]]}},"alternative-id":["10.1002\/anie.201805758"],"URL":"https:\/\/doi.org\/10.1002\/anie.201805758","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2018,7,5]]},"assertion":[{"value":"2018-05-18","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2018-07-05","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}