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Recent advances across small\u2010molecule, metalloradical, cooperative, peptide, and enzymatic catalysis show that high enantioselectivity is attainable when the catalyst is engineered to exert stereocontrol precisely at the H\u2010transfer step that sets configuration. In this minireview, we organize asymmetric HAT into five regimes\u2014donation\u2010controlled termination, radical\u2010centered control, abstraction\u2010controlled HAT, cooperative bimetallic catalysis, and enzyme\u2010mediated HAT\u2014each specified by where chiral information is introduced during H\u2010transfer. Through representative cases, we illustrate how catalysts achieve enantioselection by defining radical geometry, guiding H\u2010delivery, enforcing selective hydrogen abstraction, or confining donor\u2013acceptor pairs within organized chiral environments. This mechanistic framework provides a unified lens spanning synthetic and biocatalytic systems, clarifies the distinct stereochemical logics in each regime, and highlights emerging opportunities for expanding asymmetric radical chemistry through precisely orchestrated H\u2010atom transfer.\n                  <\/jats:p>","DOI":"10.1002\/anie.202526135","type":"journal-article","created":{"date-parts":[[2026,1,25]],"date-time":"2026-01-25T07:17:46Z","timestamp":1769325466000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Where Enantioselection is Set: A Mechanistic Framework for Asymmetric Hydrogen\u2010Atom Transfer"],"prefix":"10.1002","volume":"65","author":[{"given":"Zhongyun","family":"Xu","sequence":"first","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shandong University  Jinan 250100 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