A series of oxidative addition complexes with a general formula (tBu₃P)Pd(Ar)X, as a class of precatalysts, were synthesized for challenging Suzuki–Miyaura coupling involving coupling partners, such as (i) sensitive polyfluorinated arylboronic acids or their corresponding boronic esters, (ii) sterically hindered electrophiles, and (iii) sterically hindered nucleophiles. A total of 89 examples are reported, of which 39 examples are in the Supporting Information. These precatalysts, in particular (tBu₃P)Pd(4-CF₃Ph)Br, were demonstrated to be powerful catalytic systems in general for cross coupling reactions in comparison to the in situ systems created by mixing tBu₃P ligand with a palladium precursor. The precatalysts are also superior to the other monoligated systems, such as Buchwald’s biaryl based G3 or G4 palladacycles. In addition, the (tBu₃P)Pd(4-CF₃Ph)Br precatalyst is also highly effective for the second most popular coupling reaction, namely the Buchwald–Hartwig coupling. In this study, hindered and electron-deficient amines were coupled with hindered (hetero)aryl bromides and chlorides with 34 examples, of which 8 are in the Supporting Information. Interestingly, the results obtained for both C–C and C–N couplings were on par with or superior to that of the “state-of-the-art” catalysts containing Ad₃P and Np₃P ligands for the same or similar substrates, suggesting that it is not all about the ligands.

中文翻译：

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不仅仅是配体：通过氧化加成络合物作为预催化剂探索 tBu3P 的隐藏潜力

合成了一系列具有通式 ( t Bu ₃ P)Pd(Ar)X 的氧化加成配合物，作为一类预催化剂，用于挑战涉及偶联伙伴的 Suzuki-Miyaura 偶联，例如 (i) 敏感的多氟芳基硼酸或它们相应的硼酸酯，(ii) 位阻亲电试剂，和 (iii) 位阻亲核试剂。总共报告了 89 个示例，其中 39 个示例在 Supporting Information 中。这些预催化剂，特别是 ( t Bu ₃ P)Pd(4-CF ₃ Ph)Br，与通过混合t创建的原位系统相比，被证明是通常用于交叉偶联反应的强大催化系统具有钯前体的Bu _{3 P 配体。}预催化剂也优于其他单配体系统，例如 Buchwald 的基于双芳基的 G3 或 G4 钯环。此外，( t Bu ₃ P)Pd(4-CF ₃ Ph)Br 预催化剂对于第二个最流行的偶联反应，即 Buchwald-Hartwig 偶联也非常有效。在这项研究中，受阻胺和缺电子胺与受阻（杂）芳基溴化物和氯化物偶联，有 34 个实例，其中 8 个在支持信息中。_{有趣的是，C-C 和 C-N 偶联获得的结果与包含 Ad 3} P 和 Np ₃的“最先进”催化剂相当或优于其结果相同或相似底物的 P 配体，表明它不全是关于配体的。