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The known methods for direct synthesis of these compounds via coupling with (hetero)aryl halides suffer from narrow reaction scope. Herein, we report that the combination of copper salts and oxalic diamides enables the coupling of a variety of (hetero)aryl halides (Cl, Br) and ethyl cyanoacetate under mild conditions, affording \u03b1\u2010(hetero)arylacetonitriles via one\u2010pot decarboxylation. Additionally, the CuBr\/oxalic diamide catalyzed coupling of (hetero)aryl bromides with \u03b1\u2010alkyl\u2010substituted ethyl cyanoacetates proceeds smoothly at 60\u2009\u00b0C, leading to the formation of \u03b1\u2010alkyl (hetero)arylacetonitriles after decarboxylation. The method features a general substrate scope and is compatible with various functionalities and heteroaryls.<\/jats:p>","DOI":"10.1002\/anie.202014638","type":"journal-article","created":{"date-parts":[[2020,12,28]],"date-time":"2020-12-28T22:38:42Z","timestamp":1609195122000},"page":"7082-7086","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":62,"title":["Assembly of \u03b1\u2010(Hetero)aryl Nitriles via Copper\u2010Catalyzed Coupling Reactions with (Hetero)aryl Chlorides and Bromides"],"prefix":"10.1002","volume":"60","author":[{"given":"Ying","family":"Chen","sequence":"first","affiliation":[{"name":"School of Physical Science and Technology ShanghaiTech University 393 Middle Huaxia Road Shanghai 201210 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lanting","family":"Xu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Bioorganic &amp; Natural Products Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Lu Shanghai 200032 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yongwen","family":"Jiang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Bioorganic &amp; Natural Products Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Lu Shanghai 200032 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1721-7551","authenticated-orcid":false,"given":"Dawei","family":"Ma","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Bioorganic &amp; Natural Products Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Lu Shanghai 200032 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2021,2,17]]},"reference":[{"key":"e_1_2_2_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/jm100762r"},{"key":"e_1_2_2_2_1","unstructured":"\u00a0"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201403201"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2004.04.029"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF00170215"},{"key":"e_1_2_2_6_1","unstructured":"\u00a0"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja026584h"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200351954"},{"key":"e_1_2_2_8_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200351954"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja053027x"},{"key":"e_1_2_2_10_1","unstructured":"\u00a0"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja201743j"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol503479g"},{"key":"e_1_2_2_13_1","unstructured":"For selected references on Pd-catalyzed coupling of aryl halides with \u03b1 \u03b1-disubstituted nitriles see:"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201402466"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b11610"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.8b02238"},{"key":"e_1_2_2_17_1","unstructured":"\u00a0"},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201006763"},{"key":"e_1_2_2_18_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201006763"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201406765"},{"key":"e_1_2_2_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201406765"},{"key":"e_1_2_2_20_1","unstructured":"\u00a0"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201905623"},{"key":"e_1_2_2_21_3","doi-asserted-by":"crossref","first-page":"11603","DOI":"10.1002\/ange.201905623","volume":"131","year":"2019","journal-title":"Angew. 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