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Moreover, the versatility of this reaction is illustrated by its successful application in the late-stage functionalization and formal synthesis of various representative chiral natural products and pharmaceutical scaffolds. This strategy eliminates the need for synthesizing chiral noncanonical aryl alanines before peptide formation, and the hydrogenation reaction does not result in racemization or epimerization. The underlying mechanism was extensively explored through deuterium labeling, control experiments, HRMS identification, and UV-Vis spectroscopy, which supported a reasonable Co\n            <jats:sup>I<\/jats:sup>\n            \/Co\n            <jats:sup>III<\/jats:sup>\n            catalytic cycle. Notably, acetic acid and methanol serve as safe and cost-effective hydrogen sources, while indium powder acts as the terminal electron source.\n          <\/jats:p>","DOI":"10.1126\/sciadv.adk4950","type":"journal-article","created":{"date-parts":[[2023,12,20]],"date-time":"2023-12-20T18:58:40Z","timestamp":1703098720000},"update-policy":"https:\/\/doi.org\/10.34133\/aaas_crossmark","source":"Crossref","is-referenced-by-count":8,"title":["Expedient and divergent synthesis of unnatural peptides through cobalt-catalyzed diastereoselective umpolung hydrogenation"],"prefix":"10.1126","volume":"9","author":[{"ORCID":"https:\/\/orcid.org\/0009-0005-3321-3664","authenticated-orcid":true,"given":"Xinjian","family":"Song","sequence":"first","affiliation":[{"name":"Engineering Research Center of Coptis Development and Utilization, Ministry of Education, College of Pharmaceutical Sciences, Southwest University, 2 Tiansheng Road, Chongqing, 400715, P. R. 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