Enantioselective C-P Bond Formation through C(sp3)-H Functionalization

Ardevines, Sandra (Universidad de Zaragoza) ; Horn, Devan ; Alegre-Requena, Juan V. ; González-Jiménez, Marta ; Gimeno, M. Concepción ; Marqués-López, Eugenia (Universidad de Zaragoza) ; Herrera, Raquel P.

Resumen: 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.

Idioma: Inglés

DOI: 10.1002/adsc.202300393

Año: 2023

Publicado en: Advanced Synthesis and Catalysis 365, 13 (2023), 2152-2158
ISSN: 1615-4150

Factor impacto JCR: 4.4 (2023)

Categ. JCR: CHEMISTRY, ORGANIC rank: 8 / 58 = 0.138 (2023) - Q1 - T1
Categ. JCR: CHEMISTRY, APPLIED rank: 19 / 74 = 0.257 (2023) - Q2 - T1

Factor impacto CITESCORE: 9.4 - Organic Chemistry (Q1) - Catalysis (Q2)

Factor impacto SCIMAGO: 1.02 - Organic Chemistry (Q1) - Catalysis (Q2)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E07-23R
Financiación: info:eu-repo/grantAgreement/ES/MCIN/AEI/PID2020-117455GB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2019-104379RB-C21

Tipo y forma: Article (Published version)

Área (Departamento): Área Química Orgánica (Dpto. Química Orgánica)