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

Autor: Mario Martínez‐Mingo, Andrés García‐Viada, Daniel Sowa Prendes, Inés Alonso, Nuria Rodríguez, Ramón Gómez Arrayás, Juan C. Carretero
Přispěvatelé: UAM. Departamento de Química Orgánica
Rok vydání: 2022
Předmět:
Zdroj: Angewandte Chemie International Edition. 61
ISSN: 1521-3773
1433-7851
DOI: 10.1002/anie.202209865
Popis: The selective δ-C(sp3)−H acetoxylation of N-(SO2Py)-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 SO2Py 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-CH2. Experimental and DFT mechanistic studies provide important insights about the mechanism and the underlying factors controlling the chemo- and regioselectivity
We thank the Ministerio de Ciencia e Innovación (MICINN) and Fondo Europeo de Desarrollo Regional (FEDER, UE) for financial support (Agencia Estatal de Investigación/Project PGC2018-098660-B-I00). M.M.-M. thanks MINECO for a FPI predoctoral fellowship and D.S.P. thanks Fonds der chemischen Industrie FCI (PhD fellowship) for financial support
Databáze: OpenAIRE
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