Nickel‐Catalyzed Amination of Aryl Nitriles for Accessing Diarylamines through C−CN Bond Activation

Ke, Wu; Rong, Qiang; Sun, Nan; Hu, Baoxiang; Shen, Zhenlu; Jin, Liqun; Hu, Xinquan

doi:10.1002/adsc.202100641

Cited by 5 publications

(5 citation statements)

References 31 publications

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“…Recently, Hu and co-workers successfully employed aryl nitriles as electrophiles to access diverse diarylamines via effective CÀ CN bond activation. [47] Aryl nitriles smoothly coupled with anilines in presence of NiCl 2 (dppf) as the catalyst, KHMDS as the base in toluene at 150 °C for 8 h to productively furnish the desired aminated products (Scheme 27). They expanded the scope of the method with different aromatic and heteroaromatic nitriles with various aniline derivatives that afforded 15-95 % of the diarylamines.…”

Section: Other Electrophilesmentioning

confidence: 99%

“…Recently, Hu and co‐workers successfully employed aryl nitriles as electrophiles to access diverse diarylamines via effective C−CN bond activation [47] . Aryl nitriles smoothly coupled with anilines in presence of NiCl 2 (dppf) as the catalyst, KHMDS as the base in toluene at 150 °C for 8 h to productively furnish the desired aminated products (Scheme 27).…”

Section: Homogeneous Ni‐catalysed Aminationsmentioning

confidence: 99%

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Nickel‐Catalysed Amination of Arenes and Heteroarenes

2022

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C(sp 2 )À N cross-coupling is one of the most powerful transformations in organic synthesis to construct highly ubiquitous anilines and aniline derivatives. The dominance of Pd-and Cubased catalytic systems is evident in the field for a long time. However, Ni-catalysed methodologies to achieve this reaction have grown gradually as sustainable alternatives in the last two decades. Recent reports of highly applicable photocatalytic and electrochemical amination strategies sufficiently enhanced the potential of Ni-catalysed aminations. This review summarizes the advancement of this cross-coupling reaction as a general and efficient method over the last 5 years.

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Section: Other Electrophilesmentioning

confidence: 99%

Section: Homogeneous Ni‐catalysed Aminationsmentioning

confidence: 99%

Nickel‐Catalysed Amination of Arenes and Heteroarenes

2022

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“…In this case, preformed lithium amide salt was replaced by strong potassium hexamethyldisilazane (KHMDS) base (Scheme 19). [39] Various aromatic and heteroaromatic nitriles were compatible to couple with substituted anilines to produce a diverse range of diarylamines in moderate to excellent yields. Interestingly, this protocol doesn't require any additive to activate the C−CN bond.…”

Section: Decyanative Functionalizationmentioning

confidence: 99%

Recent Developments in Hydrodecyanation and Decyanative Functionalization Reactions

Paul

Patra

2021

Asian J Org Chem

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Nitrile is one of the ubiquitous functional groups in natural products and polymer industry. It is often used as a versatile building block in synthetic chemistry. Classically, nitrile group is used for alpha functionalization, orthoÀ CÀ H activation and as a precursor for amine or carbonyl functionalities. With the development of various transition metal catalyzed methods, in the last two decades, nitrile group has emerged as a source of carbon synthons through CÀ CN bond activation despite of its high bond energy. In this review we have summarized all recent developments involving the carbon synthons arising from the cleavage of CÀ CN bonds. Depending on the fate of the carbon center after cleavage, all the reactions are classified in two major categories for the ease of discussion: 1) decyanation (removal of the nitrile group) and 2) decyanative functionalization (replacement of the nitrile group). Finally, current limitations in CÀ CN bond activation strategies and future prospects are discussed.

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“…通过考察多种手性二醇配体, 发现 L8 具有最优的产率与 ee 值. 该反应在温和的反应 2021 年, 胡信全等 [25] Mizoroki-Heck 反应 [27] 被认为是构建烯烃化产物最有力的工具之一. 2010 年, Chatani 课题组 [28] 随后该课题组 [29] 继续报道了一种铑催化芳基氰化物碳-氰基键断裂制备芳基硼酸盐的新方法(Scheme 11).…”

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Recent Advances in the Transformation Reactions of Aromatic Nitriles via C—CN Bond Cleavage

Miao¹,

Yao²

2023

Chinese Journal of Organic Chemistry

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Aromatic nitriles are one of the ubiquitous versatile materials in organic synthesis, and also a class of important synthetic intermediates for a wide range of applications in pharmaceuticals, agricultural chemicals, dyes, spices, and functional materials. However, the C-CN bond of aryl nitriles has rarely been considered as a valuable reaction site due to the high thermodynamic stability. Therefore, the development of simple and efficient methods to catalyze the C-CN bond transformation of aryl nitriles has become one of the hot research topics in recent years. In this review, the recent advances in the transformation reactions of aromatic nitriles via C-CN bond cleavage in the past decade are summarized and classified according to different reaction mechanisms, mainly including transition metal-mediated/catalyzed C-CN transformation, free radical-mediated C-CN transformation, Lewis acid, base or Brønsted acid-mediated C-CN transformation. The reaction substrate compatibility, mechanism, applications, advantages and limitations in this field are also discussed in detail. Keywords aromatic nitriles; C-CN bond cleavage; transformation reaction; classification of reaction mechanisms 氰基是由碳和氮原子通过叁键相连接的基团(即 CN), 含有氰基的化合物称为腈. 有机氰化物是一类基础且重要的合成原料和中间体, 在有机合成领域具有重要的作用. 如利用氰化物可容易获得其他更具价值的官能团化合物, 包括酰胺、酯基、醛基、羧酸以及伯胺等官能团 [1] , 也广泛应用于药物、农用化学品、精细化学品、染料、香料以及功能材料等领域 [2] . 芳香腈类化合物原料很容易获得, 通常采用过渡金属催化芳烃卤代物的氰基化 [3] 或者芳烃 C-H 键活化进行氰基化反应以及酰胺脱水等 [4] . 碳碳键的形成和转化是众多化学爱好者的研究课题. 然而 C-CN 键具有较高的键能(＞400 kJ/mol), 其断裂反应一直是研究难点之一. 总的来说, 在交叉偶联中使用芳香腈(ArCN)的情况较少, 以往大多利用过渡金属催化芳基卤化物或芳香亲核取代(S N Ar)实现芳基化偶合反应 [5] .

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Nickel‐Catalyzed Amination of Aryl Nitriles for Accessing Diarylamines through C−CN Bond Activation

Cited by 5 publications

References 31 publications

Nickel‐Catalysed Amination of Arenes and Heteroarenes

Nickel‐Catalysed Amination of Arenes and Heteroarenes

Recent Developments in Hydrodecyanation and Decyanative Functionalization Reactions

Recent Advances in the Transformation Reactions of Aromatic Nitriles via C—CN Bond Cleavage

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