{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T00:00:52Z","timestamp":1789603252819,"version":"build-2803163510"},"reference-count":39,"publisher":"Wiley","issue":"11","license":[{"start":{"date-parts":[[2019,2,6]],"date-time":"2019-02-06T00:00:00Z","timestamp":1549411200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100000057","name":"National Institute of General Medical Sciences","doi-asserted-by":"publisher","award":["R01-GM062871"],"award-info":[{"award-number":["R01-GM062871"]}],"id":[{"id":"10.13039\/100000057","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000057","name":"National Institute of General Medical Sciences","doi-asserted-by":"publisher","award":["F32-GM116234"],"award-info":[{"award-number":["F32-GM116234"]}],"id":[{"id":"10.13039\/100000057","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2019,3,11]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Metal\u2010catalyzed enantioconvergent cross\u2010coupling reactions of alkyl electrophiles are emerging as a powerful tool in asymmetric synthesis. To date, high enantioselectivity has been limited to couplings of electrophiles that bear a directing group or a proximal p\/\u03c0 orbital. Herein, we demonstrate for the first time that enantioconvergent cross\u2010couplings can be achieved with electrophiles that lack such features; specifically, we establish that a chiral nickel catalyst can accomplish Negishi reactions of racemic \u03b1\u2010halosilanes with alkylzinc reagents with good enantioselectivity under simple and mild conditions, thereby providing access to enantioenriched organosilanes, an important class of target molecules.<\/jats:p>","DOI":"10.1002\/anie.201814208","type":"journal-article","created":{"date-parts":[[2019,1,16]],"date-time":"2019-01-16T20:32:11Z","timestamp":1547670731000},"page":"3571-3574","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":84,"title":["Enantioconvergent Cross\u2010Couplings of Alkyl Electrophiles: The Catalytic Asymmetric Synthesis of Organosilanes"],"prefix":"10.1002","volume":"58","author":[{"given":"Gregg M.","family":"Schwarzwalder","sequence":"first","affiliation":[{"name":"Division of Chemistry and Chemical Engineering California Institute of Technology  Pasadena CA 91125 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Carson D.","family":"Matier","sequence":"additional","affiliation":[{"name":"Division of Chemistry and Chemical Engineering California Institute of Technology  Pasadena CA 91125 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0927-680X","authenticated-orcid":false,"given":"Gregory C.","family":"Fu","sequence":"additional","affiliation":[{"name":"Division of Chemistry and Chemical Engineering California Institute of Technology  Pasadena CA 91125 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2019,2,6]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aaf7230"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.7b00212"},{"key":"e_1_2_2_4_1","unstructured":"For related reviews see:"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00731"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1007\/s41061-015-0002-2"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00162"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9409804"},{"key":"e_1_2_2_9_1","unstructured":"For examples of applications to the synthesis of natural products see:"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201106762"},{"key":"e_1_2_2_10_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201106762"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201601958"},{"key":"e_1_2_2_11_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201601958"},{"key":"e_1_2_2_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b04725"},{"key":"e_1_2_2_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/f19767202908"},{"key":"e_1_2_2_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b11707"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00382a045"},{"key":"e_1_2_2_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja067552n"},{"key":"e_1_2_2_16_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bmcl.2012.03.054"},{"key":"e_1_2_2_17_1","unstructured":"For reviews see:"},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.7b00718"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.4155\/fmc-2016-0193"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1007\/7355_2014_55"},{"key":"e_1_2_2_21_1","unstructured":"For examples of early studies of the catalytic asymmetric synthesis of related chiral silanes (two alkyl substituents on the stereogenic carbon atom that bears silicon) see:"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00224a057"},{"key":"e_1_2_2_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00026a044"},{"key":"e_1_2_2_24_1","unstructured":"For recent examples of (and leading references to) the catalytic asymmetric synthesis of related chiral silanes (two alkyl substituents on the stereogenic carbon atom that bears silicon) see:"},{"key":"e_1_2_2_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b01638"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201700162"},{"key":"e_1_2_2_27_1","unstructured":"\u00a0"},{"key":"e_1_2_2_28_2","unstructured":"For entries\u200512\u201314 of Table\u20052 we observed enantioselectivities that are comparable to the other examples described in this study indicating that an aryl substituent on silicon is not essential for enantioselectivity and that the aryl substituent is not likely serving as a directing group;"},{"key":"e_1_2_2_29_2","unstructured":"for the electrophile illustrated in entry\u200512 of Table\u20052 when Si is replaced with C essentially no cross-coupling is observed under our standard conditions."},{"key":"e_1_2_2_30_1","unstructured":"When PhZnBr in THF is employed as the nucleophile under otherwise identical conditions essentially no cross-coupling is observed."},{"key":"e_1_2_2_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja508718m"},{"key":"e_1_2_2_32_1","unstructured":"Consistent with the hypothesis that an organic radical is an intermediate in these nickel-catalyzed cross-couplings the model reaction (Table\u20051) does not proceed (<1\u2009% yield) in the presence of TEMPO (0.4\u2005equiv)."},{"key":"e_1_2_2_33_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201702402"},{"key":"e_1_2_2_33_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201702402"},{"key":"e_1_2_2_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja105148g"},{"key":"e_1_2_2_35_1","unstructured":"This work was presented in part at the 254th National Meeting of the American Chemical Society (Washington D.C.) in August 2017."}],"container-title":["Angewandte Chemie International 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