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Palladium‐Catalyzed PIDA‐Mediated δ‐C(sp(3))−H Acetoxylation of Amino Acid Derivatives: Overriding Competitive Intramolecular Amination

The selective δ‐C(sp(3))−H acetoxylation of N‐(SO(2)Py)‐protected amino acid derivatives has been accomplished by using palladium‐catalysis and PhI(OAc)(2) (PIDA) as both terminal oxidant and acetoxy source. The distinct structural and electronic features of the SO(2)Py compared to more traditional...

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Detalles Bibliográficos
Autores principales: Martínez‐Mingo, Mario, García‐Viada, Andrés, Prendes, Daniel Sowa, Alonso, Inés, Rodríguez, Nuria, Arrayás, Ramón Gómez, Carretero, Juan C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9828559/
https://www.ncbi.nlm.nih.gov/pubmed/36177787
http://dx.doi.org/10.1002/anie.202209865
Descripción
Sumario:The selective δ‐C(sp(3))−H acetoxylation of N‐(SO(2)Py)‐protected amino acid derivatives has been accomplished by using palladium‐catalysis and PhI(OAc)(2) (PIDA) as both terminal oxidant and acetoxy source. The distinct structural and electronic features of the SO(2)Py compared to more traditional carbonyl‐based directing groups is essential to override the otherwise more favourable competitive intramolecular C−H amination. The δ‐site selectivity predominates over traditionally more favorable 5‐membered cyclopalladation at competitive γ‐CH(2). Experimental and DFT mechanistic studies provide important insights about the mechanism and the underlying factors controlling the chemo‐ and regioselectivity.