Enantioselective C−P Bond Formation through C(sp³)−H Functionalization,*   Ardevines, S.; Horn, D.; Alegre-Retquena, J. V.; González-Jiménez, M.; Gimeno, M. C.; Marqués-López, E.; Herrera, R. P. Adv. Synth. Catal. 2023, 365, 2152–2158. DOI: 10.1002/adsc.202300393. *A previous version of this manuscript has been deposited on a preprint server (DOI: 10.26434/chemrxiv-2023-v3vl0).

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Abstract. An 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.