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Phenalenyl-ruthenium synergism for effectual catalytic transformations of primary amines to amides
Dalton Transactions ( IF 3.5 ) Pub Date : 2024-07-25 , DOI: 10.1039/d4dt01760a Nilaj Bandopadhyay 1 , Krishnendu Paramanik 1 , Gayetri Sarkar 1 , Suvojit Roy 1 , Subhra Jyoti Panda 2 , Chandra Shekhar Purohit 2 , Bhaskar Biswas 1 , Hari Sankar Das 1
Dalton Transactions ( IF 3.5 ) Pub Date : 2024-07-25 , DOI: 10.1039/d4dt01760a Nilaj Bandopadhyay 1 , Krishnendu Paramanik 1 , Gayetri Sarkar 1 , Suvojit Roy 1 , Subhra Jyoti Panda 2 , Chandra Shekhar Purohit 2 , Bhaskar Biswas 1 , Hari Sankar Das 1
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The synthesis of amides holds great promise owing to their impeccable contributions as building blocks for highly valued functional derivatives. Herein, we disclose the design, synthesis and crystal structure of a mixed-ligand ruthenium(II) complex, [Ru(η6-Cym)(O,O-PLY)Cl], (1) where Cym = 1-isopropyl-4-methyl-benzene and O,O-PLY = deprotonated form of 9-hydroxy phenalenone (HO,O-PLY). The complex catalyzes the aerobic oxidation of various primary amines (RCH2NH2) to value-added amides (RCONH2) with excellent selectivity and efficiency under relatively mild conditions with common organic functional group tolerance. Structural, electrochemical, spectroscopic, and computational studies substantiate that the synergism between the redox-active ruthenium and π-Lewis acidic PLY moieties facilitate the catalytic oxidation of amines to amides. Additionally, the isolation and characterization of key intermediates during catalysis confirm two successive dehydrogenation steps leading to nitrile, which subsequently transform to the desired amide through hydration. The present synthetic approach is also extended to substitution-dependent tuning at PLY to tune the electronic nature of 1 and to assess substituent-mediated catalytic performance. The effect of substitution at the PLY moiety (5th position) leads to structural isomers, which were further evaluated for the catalytic transformations of amine to amides under similar reaction conditions.
中文翻译：
苯烯基-钌协同作用可有效催化伯胺转化为酰胺
酰胺的合成具有广阔的前景，因为它们作为高价值功能衍生物的构建模块具有无可挑剔的贡献。在此，我们公开了混合配体钌( II )络合物的设计、合成和晶体结构，[Ru(η 6 -Cym)(O,O-PLY)Cl]，( 1 )，其中Cym = 1-异丙基- 4-甲基苯和 O,O-PLY = 9-羟基苯烯酮 (HO,O-PLY) 的去质子化形式。该配合物可在相对温和的条件下催化各种伯胺（RCH 2 NH 2 ）有氧氧化为增值酰胺（RCONH 2 ），具有优异的选择性和效率，具有常见的有机官能团耐受性。结构、电化学、光谱和计算研究证实，氧化还原活性钌和 π-Lewis 酸性 PLY 部分之间的协同作用促进胺催化氧化为酰胺。此外，催化过程中关键中间体的分离和表征证实了两个连续的脱氢步骤，导致腈，随后通过水合转化为所需的酰胺。目前的合成方法还扩展到 PLY 的取代依赖性调节，以调节1的电子性质并评估取代基介导的催化性能。 PLY 部分（第5 位）的取代效应会产生结构异构体，并进一步评估了在类似反应条件下胺向酰胺的催化转化。
更新日期：2024-07-25
中文翻译：
苯烯基-钌协同作用可有效催化伯胺转化为酰胺
酰胺的合成具有广阔的前景，因为它们作为高价值功能衍生物的构建模块具有无可挑剔的贡献。在此，我们公开了混合配体钌( II )络合物的设计、合成和晶体结构，[Ru(η 6 -Cym)(O,O-PLY)Cl]，( 1 )，其中Cym = 1-异丙基- 4-甲基苯和 O,O-PLY = 9-羟基苯烯酮 (HO,O-PLY) 的去质子化形式。该配合物可在相对温和的条件下催化各种伯胺（RCH 2 NH 2 ）有氧氧化为增值酰胺（RCONH 2 ），具有优异的选择性和效率，具有常见的有机官能团耐受性。结构、电化学、光谱和计算研究证实，氧化还原活性钌和 π-Lewis 酸性 PLY 部分之间的协同作用促进胺催化氧化为酰胺。此外，催化过程中关键中间体的分离和表征证实了两个连续的脱氢步骤，导致腈，随后通过水合转化为所需的酰胺。目前的合成方法还扩展到 PLY 的取代依赖性调节，以调节1的电子性质并评估取代基介导的催化性能。 PLY 部分（第5 位）的取代效应会产生结构异构体，并进一步评估了在类似反应条件下胺向酰胺的催化转化。
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