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By using a chiral pyridoxal as carbonyl catalyst, we have successfully realized direct asymmetric \u03b1\u2010C\u2212H addition of N\u2010unprotected propargylic amines to trifluoromethyl ketones, producing a broad range of chiral alkynyl \u03b2\u2010aminoalcohols in 54\u201384\u2009% yields with excellent stereoselectivities (up to 20\u2009:\u20091 dr and 99\u2009% ee). The \u03b1 C\u2212H bonds of propargylic amines are greatly activated by the pyridoxal catalyst via the formation of an imine intermediate, resulting in the increase of acidity by up to 10<jats:sup>22<\/jats:sup>\u2005times (from p<jats:italic>K<\/jats:italic><jats:sub>a<\/jats:sub>\u200542.6 to p<jats:italic>K<\/jats:italic><jats:sub>a<\/jats:sub>\u200520.1), which become acidic enough to be deprotonated under mild conditions for the asymmetric addition. This work presented an impressive example for asymmetric functionalization of inert C\u2212H bonds enabled by an organocatalyst.<\/jats:p>","DOI":"10.1002\/anie.202206111","type":"journal-article","created":{"date-parts":[[2022,10,10]],"date-time":"2022-10-10T02:04:01Z","timestamp":1665367441000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":38,"title":["Direct Asymmetric \u03b1\u2010C\u2212H Addition of N\u2010unprotected Propargylic Amines to Trifluoromethyl Ketones by Carbonyl Catalysis"],"prefix":"10.1002","volume":"61","author":[{"given":"Pengwei","family":"Ji","sequence":"first","affiliation":[{"name":"The Education Ministry Key Lab of Resource Chemistry Shanghai Key Laboratory of Rare Earth Functional Materials Shanghai Frontiers Science Center of Biomimetic Catalysis Shanghai Normal University Shanghai 200234 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