Synthesis of ß-Aryl-a,ß-Dehydroaminophosphonates by Pd-Catalyzed Fujiwara–Moritani C-C Coupling

Sáez, Javier ; Dalmau, David ; Sayago, Francisco J. (Universidad de Zaragoza) ; Urriolabeitia, Esteban P.

Resumen: The treatment of diethyl α,β‐dehydroaminophosphonate 1 with various arenes (ArH=toluene 2 a, benzene 2 b, anisole 2 c, bromobenzene 2 d, chlorobenzene 2 e, benzyl alcohol 2 f, p‐xylene 2 g) in acetic acid (AcOH) at 120 °C for 8 h in the presence of Pd(OAc)2 (10 % mol, OAc=acetate) and AgOAc (3.4 equivalents) results in the formation of the corresponding β‐aryl derivatives E‐Ar(H)C=C(NHAc)P(O)(OEt)2 3 a–3 g. The reaction proceeds through double C−H activation (arene and alkene) and subsequent C−C oxidative coupling (Fujiwara–Moritani reaction), processes catalyzed by Pd and assisted by Ag. The obtained products 3 a–3 g are isosteric analogs of phenylalanine and are obtained with high selectivity. Thus, geometrical E‐isomers have been obtained in all studied cases, however mixtures of ortho‐/meta‐/para‐isomers are observed when the activated position in the starting arene 2 is considered.

Idioma: Inglés

DOI: 10.1002/ejoc.202400146

Año: 2024

Publicado en: European Journal of Organic Chemistry 27, 18 (2024), e202400146 [6 p.]
ISSN: 1434-193X

Factor impacto JCR: 2.7 (2024)

Categ. JCR: CHEMISTRY, ORGANIC rank: 16 / 57 = 0.281 (2024) - Q2 - T1

Factor impacto CITESCORE: 4.3 - Organic Chemistry (Q2) - Physical and Theoretical Chemistry (Q3)

Factor impacto SCIMAGO: 0.558 - Physical and Theoretical Chemistry (Q2) - Organic Chemistry (Q2)

Financiación: info:eu-repo/grantAgreement/ES/AEI/PID2019-106394GB-I00
Financiación: info:eu-repo/grantAgreement/ES/DGA/E07-23R
Financiación: info:eu-repo/grantAgreement/ES/DGA/E17-23R
Financiación: info:eu-repo/grantAgreement/ES/MCIN/AEI/10.13039/501100011033
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2019-106394GB-I00

Tipo y forma: Artículo (Versión definitiva)

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