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The preparation of \u03b1\u2010 and \u03b2\u2010functionalized \u03b1\u2010amino nitriles from readily available scaffolds, however, remains challenging. Herein is reported a novel dual catalytic photoredox\/copper\u2010catalyzed chemo\u2010 and regioselective radical carbocyanation of 2\u2010azadienes to access functionalized \u03b1\u2010amino nitriles by using redox\u2010active esters (RAEs) and trimethylsilyl cyanide. This cascade process employs a broad scope of RAEs and provides the corresponding \u03b1\u2010amino nitrile building blocks in 50\u201395\u2009% yields (51 examples, regioselectivity &gt;95\u2009:\u20095). The products were transformed into prized \u03b1\u2010amino nitriles and \u03b1\u2010amino acids. Mechanistic studies suggest a radical cascade coupling process.<\/jats:p>","DOI":"10.1002\/anie.202300605","type":"journal-article","created":{"date-parts":[[2023,3,10]],"date-time":"2023-03-10T13:17:30Z","timestamp":1678454250000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":19,"title":["Catalytic Chemo\u2010 and Regioselective Radical Carbocyanation of 2\u2010Azadienes for the Synthesis of \u03b1\u2010Amino Nitriles"],"prefix":"10.1002","volume":"62","author":[{"given":"Shengzu","family":"Duan","sequence":"first","affiliation":[{"name":"Key Laboratory of Medicinal Chemistry for Natural Resource Ministry of Education Yunnan Provincial Center for Research &amp; Development of Natural Products School of Pharmacy Yunnan University  Kunming 650500 P. R. 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