Chemoselektive γ‐Oxidation von β,γ‐ungesättigten Amiden mit TEMPO

Heindl, Sebastian; Riomet, Margaux; Matyašovský, Ján; Lemmerer, Miran; Malzer, Nicolas; Maulide, Nuno

doi:10.1002/ange.202104023

Cited by 7 publications

(1 citation statement)

References 60 publications

(61 reference statements)

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“…Shifting focus even further from the amide carbonyl, the Maulide group developed a method for γ‐functionalisation of β,γ‐unsaturated amides 77 (Scheme 15). [33] Herein, TEMPO ((2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl) was employed, instead of the previously used N ‐oxides, thereby evoking a radical pathway. Mechanistically, the reaction is thought to proceed by TEMPO attack on the conjugated keteniminium ion 79 , generating radical intermediate 80 .…”

Section: Electrophilic Amide Activationmentioning

confidence: 99%

Challenges and Breakthroughs in Selective Amide Activation

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.

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Section: Electrophilic Amide Activationmentioning

confidence: 99%

Challenges and Breakthroughs in Selective Amide Activation

2022

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Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation

Wu,

2024

Adv Synth Catal

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Herein, we present a photoinduced deconstructive alkoxyamination of alkyl alcohols catalyzed by iron salts. This transformation involves the initiation of alkoxy radicals through chlorine radical‐induced alkoxy radical formation, followed by β‐scission and trapping of the resulting carbon radicals with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO). This reaction exhibits a broad substrate scope (40 examples), including primary and secondary alcohols that are prone to oxidation by the combination of TEMPO and iron. Mechanistic investigations have revealed that enhanced coordination of the chloride ion with the iron center inhibits the OH oxidation process, thereby enabling the tolerance of primary and secondary alcohols.

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Highly Chemoselective Transamidation of Unactivated Tertiary Amides by Electrophilic N−C(O) Activation by Amide‐to‐Acyl Iodide Re‐routing

et al. 2022

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The challenging transamidation of unactivated tertiary amides has been accomplished via cooperative acid/iodide catalysis. Most crucially, the method provides a novel manifold to re‐route the reactivity of unactivated N,N‐dialkyl amides through reactive acyl iodide intermediates, thus reverting the classical order of reactivity of carboxylic acid derivatives. This method provides a direct route to amide‐to‐amide bond interconversion with excellent chemoselectivity using equivalent amounts of amines. The combination of acid and iodide has been identified as the essential factor to activate the amide C−N bond through electrophilic catalytic activation, enabling the production of new desired transamidated products with wide substrate scope of both unactivated amides and amines, including late‐stage functionalization of complex APIs (>80 examples). We anticipate that this powerful activation mode of unactivated amide bonds will find broad‐ranging applications in chemical synthesis.

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Chemoselektive γ‐Oxidation von β,γ‐ungesättigten Amiden mit TEMPO

Cited by 7 publications

References 60 publications

Challenges and Breakthroughs in Selective Amide Activation

Challenges and Breakthroughs in Selective Amide Activation

Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation

Highly Chemoselective Transamidation of Unactivated Tertiary Amides by Electrophilic N−C(O) Activation by Amide‐to‐Acyl Iodide Re‐routing

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