Selective Reductive Removal of Ester and Amide Groups from Arenes and Heteroarenes through Nickel‐Catalyzed C−O and C−N Bond Activation

Yue, Huifeng; Guo, Lin; Lee, Shao‐Chi; Liu, Xiangqian; Rueping, Magnus

doi:10.1002/anie.201612624

Cited by 153 publications

(54 citation statements)

References 87 publications

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“…The metal-catalyzed activation reactions of amides are not limited to cross-couplingo re sterification reactions, as exemplified by Rueping and co-workers, who developedareductive removal of ester/amide groups through NÀCa ctivation.R ueping and co-workersr eported an inexpensive nickel-catalyzed reductived efunctionalization of aryl andh eteroaryl amides. [79] The authors incorporated nontoxic and air-stable PMHS as areducinga gent and dcype as al igand.Avariety of aryl and heteroaryl amides were reduced by using their established method.T he reaction mechanism involved the oxidative addition of nickel across the NÀCb ond, CO migration, and transmetalation,followed by reductive elimination and CO extrusion (Scheme 41).…”

Section: Cross-coupling and Other Reactionsmentioning

confidence: 99%

Recent Advances in the Metal‐Catalyzed Activation of Amide Bonds

Chaudhari

Gnanaprakasam

2018

Chemistry An Asian Journal

134

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The amide functional group is commonly found in peptides, proteins, pharmaceutical compounds, natural products, andp olymers.T he synthesis of amides is typically performed by using classical approaches that involvet he reaction between ac arboxylic acid and an amine in the presence of an activator.Amides are thought to be an inert functional group, because they are unsusceptible to nucleophile attack, owing to their low electrophilicity.T he reason fort his resistancei sc lear:t he resonance stability of the amide bond. However,t ransition metal catalysis can circumvent this stability by selectively rupturing the NÀCb ond of the amide, thereby facilitating further cross-couplingo ro ther reactions.Inthis Focus Review,wediscuss the recent advances in this area and present as ummary of methods that have been developed for activating the amide NÀCb ond by using precious and non-preciousmetals.

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Section: Cross-coupling and Other Reactionsmentioning

confidence: 99%

Recent Advances in the Metal‐Catalyzed Activation of Amide Bonds

Chaudhari

Gnanaprakasam

2018

Chemistry An Asian Journal

134

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“…Communications contrast, low yields were observed with the more commonly used silane, [23] formate, [24] and alkoxide [25] reducing agents. Tr ace product was observed in the absence of alcohol.…”

Section: Angewandte Chemiementioning

confidence: 89%

Nickel‐Catalyzed Domino Heck‐Type Reactions Using Methyl Esters as Cross‐Coupling Electrophiles

Zheng

Newman

2019

Angew Chem Int Ed

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While esters are frequently used as traditional electrophiles in substitution chemistry,t heir application in cross-coupling chemistry is still in its infancy.T his work demonstrates that methyl esters can be used as coupling electrophiles in Ni-catalyzed Heck-type reactions through the challenging cleavage of the C(acyl) À Ob ond under relatively mild reaction conditions at either 80 or 100 8 8C. With the s-Ni II intermediate generated from the insertion of acyl Ni II species into the tethered C=Cb ond, carbonyl-retentive products were formed by domino Heck/Suzuki-Miyaura coupling and Heck/ reduction pathwaysw hen organoboron and mild hydride nucleophiles are used.

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“…179,180 A report by Rueping and co-workers has additionally shown the possibility of conducting a complete reductive removal of amides (and esters) using nickel acetate and silanes (Scheme 46a). 181 A 2017 report by Shi and co-workers features the description of a mechanistically intriguing retro-hydroamidocarbonylation of Boc-activated amides (304), leading to the facile formation of a wide array of olefinic products (306) through b-hydride elimination of 305 (Scheme 46b). 182 Further privileged amides in selective transformations properties for (selective) transition metal-catalysed or even metalfree transformations.…”

Section: Smi 2 -Mediated Functionalisationmentioning

confidence: 99%

Amide activation: an emerging tool for chemoselective synthesis

et al. 2018

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It is textbook knowledge that carboxamides benefit from increased stabilisation of the electrophilic carbonyl carbon when compared to other carbonyl and carboxyl derivatives. This results in a considerably reduced reactivity towards nucleophiles. Accordingly, a perception has been developed of amides as significantly less useful functional handles than their ester and acid chloride counterparts. However, a significant body of research on the selective activation of amides to achieve powerful transformations under mild conditions has emerged over the past decades. This review article aims at placing electrophilic amide activation in both a historical context and in that of natural product synthesis, highlighting the synthetic applications and the potential of this approach.

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Selective Reductive Removal of Ester and Amide Groups from Arenes and Heteroarenes through Nickel‐Catalyzed C−O and C−N Bond Activation

Cited by 153 publications

References 87 publications

Recent Advances in the Metal‐Catalyzed Activation of Amide Bonds

Recent Advances in the Metal‐Catalyzed Activation of Amide Bonds

Nickel‐Catalyzed Domino Heck‐Type Reactions Using Methyl Esters as Cross‐Coupling Electrophiles

Amide activation: an emerging tool for chemoselective synthesis

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