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Herein, we report a NiH-catalyzed Markovnikov-selective hydroalkynylation of unactivated alkenes enabled by a diamine-based ligand. This operationally simple protocol provides efficient access to structurally diverse \u03b2-, \u03b3- and \u03b4-aminoalkynes from readily available alkenyl amines and alkynyl bromides under mild conditions. The practicality of this method is further demonstrated through gram-scale synthesis and late-stage functionalization of pharmaceutically relevant molecules.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c03193","type":"journal-article","created":{"date-parts":[[2026,8,10]],"date-time":"2026-08-10T12:01:59Z","timestamp":1786363319000},"page":"10641-10646","source":"Crossref","is-referenced-by-count":0,"title":["Native Amine-Directed\nNiH-Catalyzed Markovnikov Hydroalkynylation\nof Unactivated Alkenes"],"prefix":"10.1021","volume":"28","author":[{"given":"Lu","family":"Yang","sequence":"first","affiliation":[{"name":"Tianjin Normal University , , ,","place":["Tianjin, P. R. China, 300387"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yunzheng","family":"Wang","sequence":"additional","affiliation":[{"name":"Tianjin Normal University , , ,","place":["Tianjin, P. R. China, 300387"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rui","family":"He","sequence":"additional","affiliation":[{"name":"Tianjin Normal University , , ,","place":["Tianjin, P. R. China, 300387"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Weina","family":"Zhang","sequence":"additional","affiliation":[{"name":"Tianjin Normal University , , ,","place":["Tianjin, P. R. China, 300387"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Miao","family":"Qi","sequence":"additional","affiliation":[{"name":"Tianjin Normal University , , ,","place":["Tianjin, P. R. China, 300387"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xueyuan","family":"Zhang","sequence":"additional","affiliation":[{"name":"Tianjin Normal University , , ,","place":["Tianjin, P. R. 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