Reductive Arylation of Amides via a Nickel‐Catalyzed Suzuki–Miyaura‐Coupling and Transfer‐Hydrogenation Cascade

Boit, Timothy B.; Mehta, Milauni M.; Kim, Junyong; Baker, Emma L.; Garg, Neil K.

doi:10.1002/ange.202012048

“…[49] 2021, Garg et al developed the first catalytic method for the direct intermolecular addition of two distinct nucleophiles to the carbonyl group of twisted amides 140 (Scheme 23). [50,51] Therein, a CÀ C bond and a CÀ H bond were formed sequentially, via Suzuki-Miyaura cross coupling followed by transfer hydrogenation, furnishing the secondary alcohols 141 in very good yields.…”

Section: Nickel-catalysed Amide Activationmentioning

confidence: 99%

Challenges and Breakthroughs in Selective Amide Activation

Feng

¹

,

Zhang

²

,

Maulide

³

2022

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In contrast to ketones and carboxylic esters, amides are classically seen as comparatively unreactive members of the carbonyl family, owing to their unique structural and electronic features. However, recent decades have seen the emergence of research programmes focused on the selective activation of amides under mild conditions. In the past four years, this area has continued to rapidly develop, with new advances coming in at a fast pace. Several novel activation strategies have been demonstrated as effective tools for selective amide activation, enabling transformations that are at once synthetically useful and mechanistically intriguing. This Minireview comprises recent advances in the field, highlighting new trends and breakthroughs in what could be called a new age of amide activation.

show abstract

Challenges and Breakthroughs in Selective Amide Activation

Feng

¹

,

Zhang

²

,

Maulide

³

2022

Angewandte Chemie

4

0

View full text Add to dashboard Cite

In contrast to ketones and carboxylic esters, amides are classically seen as comparatively unreactive members of the carbonyl family, owing to their unique structural and electronic features. However, recent decades have seen the emergence of research programmes focused on the selective activation of amides under mild conditions. In the past four years, this area has continued to rapidly develop, with new advances coming in at a fast pace. Several novel activation strategies have been demonstrated as effective tools for selective amide activation, enabling transformations that are at once synthetically useful and mechanistically intriguing. This Minireview comprises recent advances in the field, highlighting new trends and breakthroughs in what could be called a new age of amide activation.

show abstract

Understanding the Structure‐Activity Relationship of Ni‐Catalyzed Amide C−N Bond Activation using Distortion/Interaction Analysis

Xie

¹

,

Qin

²

,

Zhang

³

et al. 2021

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Transition metal‐catalyzed amide C−N bond activation has emerged as a powerful strategy to utilize amides in synthetic transformations. The key mechanistic basis for the rational design of amide reagents is the structure‐activity relationship of amide C−N bond activation. In this work, the controlling factors of Ni/PCy3‐catalyzed amide C−N bond activation barrier are elucidated with density functional theory (DFT) calculations and distortion/interaction analysis. We found that the substrate distortion is the key factor that differentiates the amide reactivity in the C−N bond activation. The substrate distortion of amide is associated with two distinctive structure‐activity relationships. The general planar amides undergo a classic three‐membered ring oxidative addition to cleave the C−N bond, in which the C−N heterolytic bond dissociation energy has a linear relationship with the activation barrier. The twisted amides have a chelation‐assisted transition state for the amide C−N bond cleavage, and the twisted angle τ can serve as a predictive parameter for the reactivity of the twisted amides. The understanding of the structure‐activity relationship of amide C−N bond activation provides a rational and predictive basis for future reaction designs involving transition metal‐catalyzed amide C−N bond activation.

show abstract

Reductive Arylation of Amides via a Nickel‐Catalyzed Suzuki–Miyaura‐Coupling and Transfer‐Hydrogenation Cascade

Cited by 5 publications

References 107 publications

Challenges and Breakthroughs in Selective Amide Activation

Challenges and Breakthroughs in Selective Amide Activation

Challenges and Breakthroughs in Selective Amide Activation

Understanding the Structure‐Activity Relationship of Ni‐Catalyzed Amide C−N Bond Activation using Distortion/Interaction Analysis

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