Iridium-Catalyzed C(sp3)-H Borylation Using Silyl-Bipyridine Pincer Ligands
Iridium-Catalyzed C(sp3)-H Borylation Using Silyl-Bipyridine Pincer Ligands
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DOI：
10.1002/anie.202202327
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发表时间：
2022-03-29
影响因子：
16.6
通讯作者：
Kuninobu, Yoichiro
中科院分区：
文献类型：
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作者：
Kawazu, Ryohei;Torigoe, Takeru;Kuninobu, Yoichiro
建立了铱催化脂肪族化合物C(sp(3))-H硼化反应的新配体。与6-甲基-2,2 '-联吡啶和6-异丁基-2,2 '-联吡啶形成鲜明对比的是，2,2 '-联吡啶和1,10-菲罗啉衍生物具有硅氢甲基（这将产生热稳定的NNSi钳形配合物），是该反应的合适配体。其中，基于菲罗啉的NNSi钳形配体被证明是一种很好的配体，各种脂肪族化合物在Ir/NNSi钳形催化剂体系下可以有效地转化为相应的硼化产物。NNSi螯合配体表现出独特的选择性，并使铱催化的C(sp(3))-H硼化反应使用pinacolborane [H-B（引脚）]代替B-2（引脚）(2)。观察了以[IrCl(cod)](2)为载体，以喹啉为基的NNSi钳形配体形成铱配合物，并对配合物的催化活性进行了验证。
New ligands for the iridium-catalyzed C(sp(3))-H borylation of aliphatic compounds were established. In sharp contrast to 6-methyl-2,2 '-bipyridine and 6-isobutyl-2,2 '-bipyridine, 2,2 '-bipyridine and 1,10-phenanthroline derivatives bearing a hydrosilylmethyl group (which would give a thermally stable NNSi pincer complex) served as suitable ligands for the reaction. Among them, a phenanthroline-based NNSi pincer ligand was shown to be an excellent ligand, and various aliphatic compounds were efficiently converted to the corresponding borylated products using the Ir/NNSi pincer catalyst system. The NNSi pincer ligand showed unique selectivity and enabled the iridium-catalyzed C(sp(3))-H borylation using pinacolborane [H-B(pin)] instead of B-2(pin)(2). The formation of an iridium complex bearing a quinoline-based NNSi pincer ligand from [IrCl(cod)](2) was observed, and the catalytic activity of the complex was demonstrated.