doi:10.1002/adsc.202300393engArdevines, SandraHorn, DevanAlegre-Requena, Juan V.González-Jiménez, MartaGimeno, M. ConcepciónMarqués-López, EugeniaHerrera, Raquel P.Enantioselective C-P Bond Formation through C(sp3)-H FunctionalizationART-2023-134485An enantioselective C−P bond formation has been developed through a C(sp3)−H activation in an oxidation step followed by an organocatalyzed hydrophosphonylation protocol. The asymmetric organocatalytic Pudovik reaction has been achieved following a one‐pot strategy, starting from different benzylic and allylic alcohols and dibenzyl phosphite, using MnO2 as the oxidant and a chiral squaramide as organocatalyst. The scope of the reaction provides enantiomerically enriched α‐hydroxy phosphonates with yields from 40% to >95% and enantioselectivities from 64% to >99%. Furthermore, the use of this methodology has been demonstrated to form a tetrasubstituted carbon stereocenter, generating an acetophenone derivative in situ, using diphenyl phosphite. Therefore, this approach represents an asymmetric strategy for constructing chiral C−P bonds, which are of interest to the pharmaceutical industry.2023http://zaguan.unizar.es/record/12707510.1002/adsc.202300393http://zaguan.unizar.es/record/127075oai:zaguan.unizar.es:127075info:eu-repo/grantAgreement/ES/DGA/E07-23Rinfo:eu-repo/grantAgreement/ES/MCIN/AEI/PID2020-117455GB-I00info:eu-repo/grantAgreement/ES/MICINN/PID2019-104379RB-C21Advanced Synthesis and Catalysis 365, 13 (2023), 2152-2158by-nc-ndhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/info:eu-repo/semantics/openAccess