Pd-catalysed C–H functionalisation of free carboxylic acids

Dutta, Suparna; Bhattacharya, Trisha; Geffers, Finn J.; Bürger, Marcel; Werz, Daniel B.

doi:10.1039/d1sc05392b

Cited by 41 publications

(28 citation statements)

References 122 publications

(163 reference statements)

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“…Subsequently, we intended to explore the native carboxylic acid group aided C–H arylation 2p q of carbazole-3-carboxylic acid 4a (Table 2 ). Towards this end, we performed the β-C–H arylation of N -ethylcarbazole-3-carboxylic acid ( 4a ) with 6a in the presence of Pd(OAc) 2 as catalyst (6–10 mol%) and NMe 4 Cl and KOAc as additives in AcOH or TFA at 120 °C for 24 hours.…”

Section: Table 1 Screening Of Reaction Conditions For T...mentioning

confidence: 99%

Pd(II)-Catalyzed Directing-Group-Aided C–H Arylation, Alkylation, Benzylation, and Methoxylation of Carbazole-3-carboxamides toward C2,C3,C4-Functionalized Carbazoles

2023

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We report the Pd(II)-catalyzed, bidentate directing group 8-aminoquinoline or 2-(methylthio)aniline-assisted β-C-H arylation, alkylation, benzylation and methoxylation of carbazole-3-carboxamide, carbazole-2-carboxamide substrates and construction of C2,C3,C4 functionalized carbazole motifs. The Pd(II)-catalyzed β-C-H arylation reaction was attempted using different directing groups such as 8-aminoquinoline, 2-(methylthio)aniline, 4-amino-2,1,3-benzothiadiazole, 4-methoxyquinolin-8-amine and butan-1-amine. Through optimization of reactions, the 8-aminoquinoline and 2-(methylthio)aniline were found to be suitable directing groups and especially, 2-(methylthio)aniline was found to be an efficient directing group in the Pd(II)-catalyzed β-C-H arylation, alkylation, methoxylation of carbazole-3-carboxamide, carbazole-2-carboxamide substrates. An ample number of β-C-H arylated, alkylated, benzylated and methoxylated carbazole-3-carboxamides were synthesized. The structures of representative β-C(2)-H arylated carbazole and β-C(2)-H methoxylated carbazole motifs were unequivocally confirmed by the single-crystal X-ray structure analysis. Given the wide range of applications of carbazoles in chemical, materials sciences and medicinal chemistry and there have been constant efforts for developing new methods and synthesizing functionalized carbazoles. This work contributes to the expansion of the library of the C2,C3,C4 functionalized carbazole motifs through the Pd(II)-catalyzed directing group-aided site-selective β-C-H activation and functionalization of carbazole-3-carboxamides.

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Section: Table 1 Screening Of Reaction Conditions For T...mentioning

confidence: 99%

Pd(II)-Catalyzed Directing-Group-Aided C–H Arylation, Alkylation, Benzylation, and Methoxylation of Carbazole-3-carboxamides toward C2,C3,C4-Functionalized Carbazoles

2023

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“…Carboxylic acids are among the most abundant and diverse chemical building blocks available for organic synthesis, featuring prominently in naturally occurring feedstocks such as amino acids, fatty acids, and sugar acids. In addition to their classical, two-electron reactivity as nucleophiles or electrophiles, 1 2 3 4 or as directing groups for C–H activation, 5 they can serve as versatile reagents for decarboxylative 6 or decarbonylative 6s 7 cross-coupling to forge new C–C bonds. In this regard, carboxylic acids benefit not only from widespread commercial availability, but also lesser toxicity and/or increased bench-stability relative to more reactive coupling partners, such as halides or organometallics.…”

Section: Introductionmentioning

confidence: 99%

Decarboxylative, Radical C–C Bond Formation with Alkyl or Aryl Carboxylic Acids: Recent Advances

Cresswell¹,

Tibbetts²,

Askey³

et al. 2023

Synthesis

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The ubiquity of carboxylic acids as naturally-derived or man-made chemical feedstocks has spurred the development of powerful, decarboxylative C–C bond-forming transformations for organic synthesis. Carboxylic acids benefit not only from extensive commercial availability, but are stable surrogates for organohalides or organometallic reagents in transition metal-catalysed cross-coupling. Open shell reactivity of carboxylic acids (or derivatives thereof) to furnish carbon-centred radicals is proving transformative for synthetic chemistry, enabling novel and strategy-level C(sp3)–C bond disconnections with exquisite chemoselectivity. This short review will summarise several of the latest advances in this ever-expanding area.

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“…Recently, several groups successfully demonstrated γ-C-(sp 3 )À H bond functionalization of carboxylic acid and its derivatives using transition metal catalysis, [73] however δ-C(sp 3 )À H functionalization is still in its infancy. Although, few reviews are available on remote CÀ H functionalization, [74][75][76][77][78] a focused and detailed review on remote C(sp 3 )À H functionalization of carboxylic acid and its derivative was missing (Scheme 2). Hence, it is essential to summarize these reactions in a concise report to enable further research and identify future goals in this direction.…”

Section: Introductionmentioning

confidence: 99%

Transition‐Metal‐Catalyzed Remote C(sp³)−H Functionalization Of Carboxylic Acid And Its Derivatives

et al. 2022

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Carboxylic acids are ubiquitous functional groups present in many bio-relevant molecules, including drugs and amino acids. In general, αand βÀ C(sp 3 )À H bonds of carboxylic acids are easy to functionalize, contrary to remote (γ-and δ) CÀ H bonds which are difficult due to the distal location of these CÀ H bonds from the functional group. On the other hand, functionalizing an inert C(sp 3 )À H bond is another critical challenge in synthetic chemistry due to its lower acidity and reactivity. Nevertheless, the last decade has witnessed tremendous development in remote sp 3 -CÀ H bond functionalization of carboxylic acid and its derivatives. Here, in this review, we have delineated recent progress in remote γand δ-CÀ H bond functionalization of aliphatic carboxylic acids/amino acids and their derivatives. This review is further subdivided based on the type of functionalization reaction. Finally, we have presented some applications of these methodologies, such as total synthesis of hibispeptin A, etc.

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Pd-catalysed C–H functionalisation of free carboxylic acids

Abstract: Pd-catalysed C-H functionalisation of free carboxylic acid has gained significant attention over the last few years due to the predominance of carboxylic acid moieties in pharmaceuticals and agrochemicals. But their...

Cited by 41 publications

References 122 publications

Pd(II)-Catalyzed Directing-Group-Aided C–H Arylation, Alkylation, Benzylation, and Methoxylation of Carbazole-3-carboxamides toward C2,C3,C4-Functionalized Carbazoles

Pd(II)-Catalyzed Directing-Group-Aided C–H Arylation, Alkylation, Benzylation, and Methoxylation of Carbazole-3-carboxamides toward C2,C3,C4-Functionalized Carbazoles

Decarboxylative, Radical C–C Bond Formation with Alkyl or Aryl Carboxylic Acids: Recent Advances

Transition‐Metal‐Catalyzed Remote C(sp³)−H Functionalization Of Carboxylic Acid And Its Derivatives

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Pd-catalysed C–H functionalisation of free carboxylic acids

Abstract: Pd-catalysed C-H functionalisation of free carboxylic acid has gained significant attention over the last few years due to the predominance of carboxylic acid moieties in pharmaceuticals and agrochemicals. But their...

Cited by 41 publications

References 122 publications

Pd(II)-Catalyzed Directing-Group-Aided C–H Arylation, Alkylation, Benzylation, and Methoxylation of Carbazole-3-carboxamides toward C2,C3,C4-Functionalized Carbazoles

Pd(II)-Catalyzed Directing-Group-Aided C–H Arylation, Alkylation, Benzylation, and Methoxylation of Carbazole-3-carboxamides toward C2,C3,C4-Functionalized Carbazoles

Decarboxylative, Radical C–C Bond Formation with Alkyl or Aryl Carboxylic Acids: Recent Advances

Transition‐Metal‐Catalyzed Remote C(sp3)−H Functionalization Of Carboxylic Acid And Its Derivatives

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Transition‐Metal‐Catalyzed Remote C(sp³)−H Functionalization Of Carboxylic Acid And Its Derivatives