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首页> 外文期刊>Chemistry: A European journal >BippyPhos: A Single Ligand With Unprecedented Scope in the Buchwald-Hartwig Amination of (Hetero)aryl Chlorides
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BippyPhos: A Single Ligand With Unprecedented Scope in the Buchwald-Hartwig Amination of (Hetero)aryl Chlorides

机译：BippyPhos：在（杂）芳基氯化物的Buchwald-Hartwig胺化中具有空前范围的单一配体

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摘要

Over the past two decades, considerable attention has been given to the development of new ligands for the palladium-catalyzed arylation of amines and related NH-containing substrates (i.e., Buchwald-Hartwig amination). The generation of structurally diverse ligands, by research groups in both academia and industry, has facilitated the accommodation of sterically and electronically divergent substrates including ammonia, hydrazine, amines, amides, and NH heterocycles. Despite these achievements, problems with catalyst generality persist and access to multiple ligands is necessary to accommodate all of these NH-containing substrates. In our quest to address this significant limitation we identified the BippyPhos/[Pd(cinnamyl)Cl]_2 catalyst system as being capable of catalyzing the amination of a variety of functionalized (hetero)aryl chlorides, as well as bromides and tosylates, at moderate to low catalyst loadings. The successful transformations described herein include primary and secondary amines, NH heterocycles, amides, ammonia and hydrazine, thus demonstrating the largest scope in the NH-containing coupling partner reported for a single Pd/ ligand catalyst system. We also established BippyPhos/[Pd(cinnamyl)Cl]_2 as exhibiting the broadest demonstrated substrate scope for metal-catalyzed cross-coupling of (hetero)aryl chlorides with NH indoles. Furthermore, the remarkable ability of BippyPhos/[Pd-(cinnamyl)Cl]_2 to catalyze both the selective monoarylation of ammonia and the N-arylation of indoles was exploited in the development of a new onepot, two-step synthesis of N-aryl heterocycles from ammonia, orthoalkynylhalo(hetero)arenes and (hetero) aryl halides through tandem N-arylation/ hydroamination reactions. Although the scope in the NH-containing coupling partner is broad, BippyPhos/ [Pd(cinnamyl)Cl]_2 also displays a marked selectivity profile that was exploited in the chemoselective monoarylation of substrates featuring two chemically distinct NH-containing moieties.
机译：在过去的二十年中，已经为用于胺和相关的含NH的底物（即，Buchwald-Hartwig胺化）的钯催化的芳基化的新配体的开发给予了相当大的关注。学术界和工业界的研究小组都在结构上多样化的配体产生，促进了空间和电子发散性底物的容纳，这些底物包括氨，肼，胺，酰胺和NH杂环。尽管取得了这些成就，但是催化剂通用性的问题仍然存在，并且需要多种配体来容纳所有这些含NH的底物。为了解决这一重大局限性，我们确定了BippyPhos / [Pd（肉桂基）Cl] _2催化剂体系能够在中等温度下催化各种官能化的（杂）芳基氯化物以及溴化物和甲苯磺酸盐的胺化反应。催化剂用量低。本文描述的成功转化包括伯胺和仲胺，NH杂环，酰胺，氨和肼，因此证明了单个Pd /配体催化剂体系中含NH的偶合伴侣的最大作用范围。我们还建立了BippyPhos / [Pd（肉桂基）Cl] _2，显示出金属催化的（杂）芳基氯与NH吲哚的交叉偶联的最广泛的底物范围。此外，在开发新的一锅两步合成N-芳基的过程中，利用了BippyPhos / [Pd-（肉桂基）Cl] _2催化氨的选择性单芳基化和吲哚的N-芳基化的显着能力。氨，邻炔基卤（杂）芳烃和（杂）芳基卤化物通过串联N-芳基化/加氢胺化反应生成杂环。尽管含NH的偶联伙伴的范围很广，但BippyPhos / [Pd（肉桂基）Cl] _2也显示出显着的选择性特征，该特征在具有两个化学上不同的含NH部分的底物的化学选择性单芳基化中得到了利用。

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