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.

中文翻译：

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Pd 催化 Fujiwara-Moritani C−C 偶联合成 β-芳基-α,β-脱氢氨基膦酸酯

α,β-脱氢氨基膦酸二乙酯 1 用各种芳烃（ArH=甲苯 2a、苯 2b、苯甲醚 2c、溴苯 2d、氯苯 2e、苯甲醇 2f、p-二甲苯 2 g) 在乙酸 (AcOH) 中，在 Pd(OAc) 存在下，在 120 °C 下反应 8 小时2（10% mol，OAc=乙酸盐）和 AgOAc（3.4 当量）导致形成相应的 β-芳基衍生物乙‐Ar(H)C=C(NHAc)P(O)(OEt)23 a–3 g。该反应通过双 C−H 活化（芳烃和烯烃）和随后的 C−C 氧化偶联（Fujiwara-Moritani 反应）进行，该过程由 Pd 催化并由 Ag 辅助。所得产物3a-3g是苯丙氨酸的等排类似物，并且以高选择性获得。因此，几何乙在所有研究案例中都获得了异构体，但是异构体的混合物正射‐/元‐/帕拉当考虑起始芳烃 2 中的活化位置时，观察到异构体。