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Thermally Robust and Highly Active PCP Cobalt(II) Catalyst for Linear-Selective Hydroboration of Terminal and Internal Olefins
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-05-30 , DOI: 10.1021/acscatal.3c01412 Juntao Liu 1, 2 , Jiayan Du 1, 2 , Feng Yu 2, 3 , Lan Gan 2 , Guixia Liu 2 , Zheng Huang 2
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-05-30 , DOI: 10.1021/acscatal.3c01412 Juntao Liu 1, 2 , Jiayan Du 1, 2 , Feng Yu 2, 3 , Lan Gan 2 , Guixia Liu 2 , Zheng Huang 2
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We report the design and synthesis of cobalt complexes of L2X-type ligands for olefin hydroboration guided by the consideration of catalyst stability. Among the series of PCP-ligated Co(II) and Co(III) pincer complexes, the complex with iPr phosphino substituents exhibits broad scope, high functional group tolerance, and high catalytic activity at ppm catalyst loadings (17 ppm, 0.001 mol %) in the hydroboration of terminal olefins with pinacolborane (HBpin), furnishing anti-Markovnikov addition products. We also show that linear-selective hydroboration occurs with internal acyclic olefins at elevated temperatures, including those conjugated with the arene or carbonyl groups that are difficult to be achieved by previous catalysts. Such a catalytic property makes this cobalt catalyst suitable for terminally selective formal borylation of arylalkane through the dehydrogenation–hydroboration sequence. Experimental mechanistic data provide evidence for the involvement of a Co(II) hydride intermediate. Deuterium-labeling experiments show that the formation of terminal alkylboronate ester from internal olefins likely proceeds via the initial generation of secondary alkyl species, followed by chain-walking to form primary alkyl species, which then reacts with HBpin to produce the linear product and regenerate the hydride species.
中文翻译：
用于端烯烃和内烯烃线性选择性硼氢化反应的耐热、高活性 PCP 钴 (II) 催化剂
我们报道了在考虑催化剂稳定性的指导下，用于烯烃硼氢化的L 2 X型配体的钴配合物的设计和合成。在 PCP 连接的 Co(II) 和 Co(III) 钳状配合物系列中，具有i 的配合物Pr 膦基取代基在末端烯烃与频那醇硼烷 (HBpin) 的硼氢化反应中，在 ppm 催化剂负载量（17 ppm，0.001 mol%）下表现出广泛的范围、高官能团耐受性和高催化活性，提供反马可夫尼科夫加成产物。我们还表明，在高温下，内无环烯烃会发生线性选择性硼氢化反应，包括那些与芳烃或羰基共轭的烯烃，这是以前的催化剂难以实现的。这种催化特性使得这种钴催化剂适合通过脱氢-硼氢化序列对芳基烷烃进行末端选择性形式硼化。实验机理数据为 Co(II) 氢化物中间体的参与提供了证据。
更新日期：2023-05-30
中文翻译：
用于端烯烃和内烯烃线性选择性硼氢化反应的耐热、高活性 PCP 钴 (II) 催化剂
我们报道了在考虑催化剂稳定性的指导下，用于烯烃硼氢化的L 2 X型配体的钴配合物的设计和合成。在 PCP 连接的 Co(II) 和 Co(III) 钳状配合物系列中，具有i 的配合物Pr 膦基取代基在末端烯烃与频那醇硼烷 (HBpin) 的硼氢化反应中，在 ppm 催化剂负载量（17 ppm，0.001 mol%）下表现出广泛的范围、高官能团耐受性和高催化活性，提供反马可夫尼科夫加成产物。我们还表明，在高温下，内无环烯烃会发生线性选择性硼氢化反应，包括那些与芳烃或羰基共轭的烯烃，这是以前的催化剂难以实现的。这种催化特性使得这种钴催化剂适合通过脱氢-硼氢化序列对芳基烷烃进行末端选择性形式硼化。实验机理数据为 Co(II) 氢化物中间体的参与提供了证据。
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