Palladium Complexes Based on Ylide-Functionalized Phosphines (YPhos): Broadly Applicable High-Performance Precatalysts for the Amination of Aryl Halides at Room Temperature.,Chemistry - A European Journal

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Palladium Complexes Based on Ylide-Functionalized Phosphines (YPhos): Broadly Applicable High-Performance Precatalysts for the Amination of Aryl Halides at Room Temperature.
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-02-28 , DOI: 10.1002/chem.201905535
Jens Tappen ₁ , Ilja Rodstein ₁ , Katie McGuire ₁ , Angela Großjohann ₁ , Julian Löffler ₁ , Thorsten Scherpf ₁ , Viktoria H Gessner ₁

Affiliation

Palladium allyl, cinnamyl, and indenyl complexes with the ylide-substituted phosphines Cy3 P+ -C- (R)PCy2 (with R=Me (L1) or Ph (L2)) and Cy3 P+ -C- (Me)PtBu2 (L3) were prepared and applied as defined precatalysts in C-N coupling reactions. The complexes are highly active in the amination of 4-chlorotoluene with a series of different amines. Higher yields were observed with the precatalysts in comparison to the in situ generated catalysts. Changes in the ligand structures allowed for improved selectivities by shutting down β-hydride elimination or diarylation reactions. Particularly, the complexes based on L2 (joYPhos) revealed to be universal precatalysts for various amines and aryl halides. Full conversions to the desired products are reached mostly within 1 h reaction time at room temperature, thus making L2 to one of the most efficient ligands in C-N coupling reactions. The applicability of the catalysts was demonstrated for aryl chlorides, bromides and iodides together with primary and secondary aryl and alkyl amines, including gram-scale applications also with low catalyst loadings of down to 0.05 mol %. Kinetic studies further demonstrated the outstanding activity of the precatalysts with TOF over 10.000 h-1 .

中文翻译：

基于叶立德功能化膦 (YPhos) 的钯配合物：广泛适用的高性能预催化剂，用于芳基卤化物在室温下的胺化。

烯丙基、肉桂基和茚基钯与叶立德取代的膦 Cy3 P+ -C- (R)PCy2（其中 R=Me (L1) 或 Ph (L2)）和 Cy3 P+ -C- (Me)PtBu2 (L3) 的络合物制备并用作 CN 偶联反应中定义的预催化剂。该配合物在 4-氯甲苯与一系列不同胺的胺化反应中具有很高的活性。与原位生成的催化剂相比，预催化剂的产率更高。配体结构的变化可以通过关闭β-氢化物消除或二芳基化反应来提高选择性。特别是，基于 L2 (joYPhos) 的配合物被证明是各种胺和芳基卤的通用预催化剂。在室温下，大部分在 1 小时反应时间内即可完全转化为所需产物，从而使 L2 成为 CN 偶联反应中最有效的配体之一。该催化剂适用于芳基氯化物、芳基溴化物和碘化物以及伯胺、仲芳基胺和烷基胺，包括克级应用以及低至 0.05 mol% 的催化剂负载量。动力学研究进一步证明了预催化剂的出色活性，TOF 超过 10,000 h-1 。

更新日期：2020-02-28

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