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In the last years, novel transition metal\u2010based synthesis methods have been discovered, in addition to the long\u2010known use of chiral auxiliaries. Enantiomerically pure compounds with N\u2212P<jats:sup>+<\/jats:sup>\u2212X<jats:sup>\u2212<\/jats:sup> (X=O, S, BH<jats:sub>3<\/jats:sub>) motifs served as valuable reactive building blocks to provide new classes of organophosphorus derivatives, thereby preserving the stereochemical information at the phosphorus atom. Over the years, intriguing applications in organocatalysis and transition metal catalysis have been reported for some representatives. Asymmetric reductions of C=C, C=N, and C=O double bonds were feasible with selected <jats:italic>P<\/jats:italic>\u2010stereogenic aminophosphine oxides in the presence of hydrogen transfer reagents. <jats:italic>P<\/jats:italic>\u2010stereogenic aminophosphine boranes could be easily deprotected and used as ligands for various transition metals to enable catalytic asymmetric hydrogenations of olefins and imines. This review traces the emergence of a synthetically and catalytically powerful functional compound class with phosphorus\u2010centered chirality in its main lines, starting from classical approaches to modern synthesis methods to current applications.<\/jats:p>","DOI":"10.1002\/chem.202303760","type":"journal-article","created":{"date-parts":[[2023,12,6]],"date-time":"2023-12-06T20:34:28Z","timestamp":1701894868000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["A Powerful P\u2212N Connection: Preparative Approaches, Reactivity, and Applications of <i>P<\/i>\u2010Stereogenic Aminophosphines"],"prefix":"10.1002","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5538-430X","authenticated-orcid":false,"given":"Tanja","family":"Huber","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie Fakult\u00e4t f\u00fcr Chemie und Pharmazie Universit\u00e4t Regensburg  Universit\u00e4tsstra\u00dfe 31 D-93053 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9575-7430","authenticated-orcid":false,"given":"Jonathan O.","family":"Bauer","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie Fakult\u00e4t f\u00fcr Chemie und Pharmazie Universit\u00e4t Regensburg  Universit\u00e4tsstra\u00dfe 31 D-93053 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,1,15]]},"reference":[{"key":"e_1_2_10_1_1","unstructured":"For reviews see:"},{"key":"e_1_2_10_2_2","first-page":"2437","volume":"16","author":"Valentine D. 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