{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T19:47:47Z","timestamp":1791316067065,"version":"4.3.1"},"reference-count":38,"publisher":"Wiley","issue":"19","license":[{"start":{"date-parts":[[2007,4,19]],"date-time":"2007-04-19T00:00:00Z","timestamp":1176940800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2007,5,4]]},"DOI":"10.1002\/anie.200700440","type":"journal-article","created":{"date-parts":[[2007,4,19]],"date-time":"2007-04-19T12:20:34Z","timestamp":1176985234000},"page":"3556-3558","source":"Crossref","is-referenced-by-count":163,"title":["Hiyama Reactions of Activated and Unactivated Secondary Alkyl Halides Catalyzed by a Nickel\/Norephedrine Complex"],"prefix":"10.1002","volume":"46","author":[{"given":"Neil\u2005A.","family":"Strotman","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Stefan","family":"Sommer","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gregory\u2005C.","family":"Fu","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2007,4,27]]},"reference":[{"key":"e_1_2_2_1_2","unstructured":"For reviews of the Hiyama reaction see:"},{"key":"e_1_2_2_2_2","volume-title":"Metal\u2010Catalyzed Cross\u2010Coupling Reactions","author":"Denmark S. E.","year":"2004"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1007\/3-540-45313-X_3"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja047433c"},{"key":"e_1_2_2_4_3","doi-asserted-by":"publisher","DOI":"10.1021\/ja0349352"},{"key":"e_1_2_2_5_2","unstructured":"For reviews of metal\u2010catalyzed cross\u2010coupling reactions see:"},{"key":"e_1_2_2_6_2","volume-title":"Metal\u2010Catalyzed Cross\u2010Coupling Reactions","year":"2004"},{"key":"e_1_2_2_7_2","volume-title":"Handbook of Organopalladium Chemistry for Organic Synthesis","year":"2002"},{"key":"e_1_2_2_8_2","unstructured":"For recent reviews of cross\u2010coupling reactions of alkyl electrophiles see:"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200461432"},{"key":"e_1_2_2_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200461432"},{"key":"e_1_2_2_10_2","volume-title":"Topics in Organometallic Chemistry: Palladium in Organic Synthesis","author":"Netherton M. R.","year":"2005"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200404223"},{"key":"e_1_2_2_12_2","unstructured":"For reviews of chiral bipyridine and phenanthroline ligands see:"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr0101914"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.2174\/1385272033486215"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1039\/B204272J"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200390168"},{"key":"e_1_2_2_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0613761"},{"key":"e_1_2_2_18_2","unstructured":"\u00a0"},{"key":"e_1_2_2_19_2","unstructured":"In the absence of NiCl2\u22c5glyme or of norephedrine no cross\u2010coupling was observed;"},{"key":"e_1_2_2_20_2","unstructured":"the Hiyama reaction proceeded best at high concentrations (0.5\u2009M);"},{"key":"e_1_2_2_21_2","unstructured":"under these conditions neither PhSiCl3nor PhSi(OMe)3proved to be an effective coupling partner;"},{"key":"e_1_2_2_22_2","unstructured":"the cross\u2010coupling reaction did occur in the absence of 8\u2009%\u2005H2O but less efficiently; the origin of this water (or hydroxide) effect is not yet clear."},{"key":"e_1_2_2_23_2","unstructured":"Bathophenanthroline proved to be ineffective (<5\u2009% yield)."},{"key":"e_1_2_2_24_2","unstructured":"\u00a0"},{"key":"e_1_2_2_25_2","unstructured":"In preliminary experiments under our standard conditions Hiyama cross\u2010coupling reactions of hindered unactivated secondary bromides unactivated secondary chlorides and primary halides have not been efficient (<50\u2009% yield). We have not yet explored the capacity of other nickel\/amino alcohol catalysts to achieve Hiyama reactions of these families of substrates;"},{"key":"e_1_2_2_26_2","unstructured":"we can efficiently cross\u2010couple an unactivated secondary alkyl bromide (>80\u2009% yield) in the presence of an unactivated secondary alkyl chloride (<2\u2009% yield)."},{"key":"e_1_2_2_27_2","unstructured":"\u00a0"},{"key":"e_1_2_2_28_2","unstructured":"We have established that gram\u2010scale Hiyama cross\u2010coupling reactions proceed in good yield (ethyl 2\u2010chloropropionate with PhSiF3 1.44\u2005g (81\u2009%));"},{"key":"e_1_2_2_29_2","unstructured":"we could effect the selective cross\u2010coupling reaction (krel>50) of an activated secondary bromide (ethyl 2\u2010bromoisovalerate) in the presence of an unactivated secondary bromide (cyclohexyl bromide);"},{"key":"e_1_2_2_30_2","unstructured":"a preliminary study indicates that benzylic halides are not useful cross\u2010coupling partners under our standard conditions."},{"key":"e_1_2_2_31_2","unstructured":"To the best of our knowledge no examples of nickel\u2010 or palladium\u2010catalyzed cross\u2010coupling reactions of secondary \u03b1\u2010halocarbonyl compounds with aryl metal reagents (for example boron silicon tin and zinc) have been described; couplings of primary \u03b1\u2010halocarbonyl compounds appear to be limited to Suzuki reactions; for examples see:"},{"key":"e_1_2_2_32_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.1989.1405"},{"key":"e_1_2_2_33_2","doi-asserted-by":"publisher","DOI":"10.1039\/b100834j"},{"key":"e_1_2_2_34_2","doi-asserted-by":"publisher","DOI":"10.1039\/b111355k"},{"key":"e_1_2_2_35_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(03)00066-2"},{"key":"e_1_2_2_36_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(03)00586-0"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.200700440","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.200700440","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,10,16]],"date-time":"2023-10-16T20:25:51Z","timestamp":1697487951000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.200700440"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2007,4,27]]},"references-count":38,"journal-issue":{"issue":"19","published-print":{"date-parts":[[2007,5,4]]}},"alternative-id":["10.1002\/anie.200700440"],"URL":"https:\/\/doi.org\/10.1002\/anie.200700440","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2007,4,27]]}}}