Catalytic Ester and Amide to Amine Interconversion: Nickel‐Catalyzed Decarbonylative Amination of Esters and Amides by C−O and C−C Bond Activation

Yue, Huifeng; Guo, Lin; Liao, Hsuan‐Hung; Cai, Yunfei; Zhu, Chen; Rueping, Magnus

doi:10.1002/anie.201611819

Cited by 159 publications

(55 citation statements)

References 54 publications

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“…1 Based on early examples of Ni/PCy 3 -catalyzed Suzuki-Miyaura coupling with aryl esters, 2 the Ni-mediated C(sp 2 )–O bond cleavage of ester 3 has been extended to various additional electrophiles, including carbamates, 4 sulfamates, 4c,4f,4g,5 phosphates, 6 and phenolates 7 . In addition, tremendous success has been achieved in the Nickel-catalyzed C–O activation and functionalization with ethers 8 .…”

Section: Introductionmentioning

confidence: 99%

Mechanism and Origins of Ligand-Controlled Stereoselectivity of Ni-Catalyzed Suzuki–Miyaura Coupling with Benzylic Esters: A Computational Study

et al. 2017

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Nickel catalysts have shown unique ligand control of stereoselectivity in the Suzuki–Miyaura cross-coupling of boronates with benzylic pivalates and derivatives involving C(sp3)–O cleavage. The SIMes ligand produces the stereochemically inverted C–C coupling product, while the PCy3 ligand delivers the retained stereochemistry. We have explored the mechanism and origins of the ligand-controlled stereoselectivity with density functional theory (DFT) calculations. The oxidative addition determines the stereoselectivity with two competing transition states, an SN2 back-side attack type transition state that inverts the benzylic stereogenic center, and a concerted oxidative addition through a cyclic transition state which provides stereoretention. The key difference between the two transition states is the substrate-nickel-ligand angle distortion; the ligand controls the selectivity by differentiating the ease of this angle distortion. For the PCy3 ligand, the nickel-ligand interaction involves mainly σ-donation, which does not require a significant energy penalty for the angle distortion. The facile angle distortion with PCy3 ligand allows the favorable cyclic oxidative addition transition state, leading to the stereoretention. For the SIMes ligand, the extra d-p back donation from nickel to the coordinating carbene increases the rigidity of nickel-ligand bond, and the corresponding angle distortion is more difficult. This makes the concerted cyclic oxidative addition unfavorable with SIMes ligand, and the back-side SN2-type oxidative addition delivers the stereoinversion.

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Section: Introductionmentioning

confidence: 99%

Mechanism and Origins of Ligand-Controlled Stereoselectivity of Ni-Catalyzed Suzuki–Miyaura Coupling with Benzylic Esters: A Computational Study

et al. 2017

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Section: Methodsmentioning

confidence: 99%

“…With the aim to expand the nickel‐catalyzed inert bond functionalization, we recently developed direct aminations of esters and amides with imines as nucleophiles . The reactions provide primary amines but could not be extended to secondary amines as these directly result in the amide formation . For instance, use of secondary amines, such as morpholine was reported to result in the aminolysis reaction of the ester affording the corresponding morpholine amide product .…”

Section: Methodsmentioning

confidence: 99%

“…The reactions provide primary amines but could not be extended to secondary amines as these directly result in the amide formation . For instance, use of secondary amines, such as morpholine was reported to result in the aminolysis reaction of the ester affording the corresponding morpholine amide product . Additionally, very useful protocols for the direct amidation of esters with N ‐methyl anilines and nitroarenes were recently described.…”

Section: Methodsmentioning

confidence: 99%

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Synthesis of Amidines from Amides Using a Nickel‐Catalyzed Decarbonylative Amination through CO Extrusion Intramolecular Recombination Fragment Coupling

Liu

Yue

Jia

et al. 2017

Chemistry A European J

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A catalytic synthesis of amidines from amides has been established for the first time. The newly developed CO extrusion recombination process takes advantage of an inexpensive nickel(II) catalyst and provides the corresponding amidines with high efficiency. The intramolecular fragment coupling shows excellent chemoselectivity, starts from readily available amides, and provides a valuable alternative amidine synthesis protocol.

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“…The first catalytic decarbonylative amination protocol was recently developed by Rueping's group . The protocol allows the direct conversion of aroyl compounds into the corresponding amines and represents a good alternative to classical Buchwald–Hartwig aminations which make use of aryl halides.…”

Section: Carbon–heteroatom Bond Forming Reactionsmentioning

confidence: 99%

Transition‐Metal‐Catalyzed Decarbonylative Coupling Reactions: Concepts, Classifications, and Applications

Guo

Rueping

2018

Chemistry A European J

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118

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Transition metal-catalyzed decarbonylative coupling reactions have emerged as a powerful alternative to conventional cross-coupling protocols due to the advantages associated with the use of carbonyl-containing functionalities as coupling electrophiles instead of commonly used organohalides or sulfates. A wide variety of novel transformations based on this concept have been successfully achieved, including decarbonylative carbon-carbon and carbon-heteroatom bond forming reactions. In this Review, we summarize the recent progress in this field and present a comprehensive overview of metal-catalyzed decarbonylative coupling reactions with carbonyl derivatives.

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Catalytic Ester and Amide to Amine Interconversion: Nickel‐Catalyzed Decarbonylative Amination of Esters and Amides by C−O and C−C Bond Activation

Cited by 159 publications

References 54 publications

Mechanism and Origins of Ligand-Controlled Stereoselectivity of Ni-Catalyzed Suzuki–Miyaura Coupling with Benzylic Esters: A Computational Study

Mechanism and Origins of Ligand-Controlled Stereoselectivity of Ni-Catalyzed Suzuki–Miyaura Coupling with Benzylic Esters: A Computational Study

Synthesis of Amidines from Amides Using a Nickel‐Catalyzed Decarbonylative Amination through CO Extrusion Intramolecular Recombination Fragment Coupling

Transition‐Metal‐Catalyzed Decarbonylative Coupling Reactions: Concepts, Classifications, and Applications

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