Transition metal catalyzed C-H activation for the synthesis of medicinally relevant molecules: A Review

Basu, Debjit; Kumar, S. Kiran; Sudhir, Sai; Bandichhor, Rakeshwar

doi:10.1007/s12039-018-1468-6

Cited by 56 publications

(24 citation statements)

References 55 publications

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“…CH bond activation [ 1–5 ] has attracted extensive attention in organic syntheses. [ 6–11 ] Particularly, palladium‐catalyzed direct arylation involves coupling of the aryl halide with the sp 2 ‐sp 2 CH functionality to accomplish aryl–aryl bond formation.…”

Section: Methodsmentioning

confidence: 99%

Aqueous Palladium‐Catalyzed Direct Arylation Polymerization of 2‐Bromothiophene Derivatives

Lin

Sun

Yang

et al. 2020

Macromol. Rapid Commun.

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Conjugated polyelectrolytes have been utilized in applications including chemical/biosensing, [30][31][32] cell imaging, [33][34][35] and disease diagnosis/therapy. [36,37] Their synthesis comprises the preparation of organic-soluble conjugated polymers followed by post-functionalization. A typical post-functionalization reaction is the nucleophilic substitution of an alkyl-bromide with amines to afford ammonium salts, which render the resultant conjugated polyelectrolytes aqueous soluble. However, post-functionalization exhibits poor conversion with many unreacted reaction sites. Aqueous polymerization of water-soluble monomers is an alternate approach realized through Heck, [38,39] Sonogashira, [40,41] Suzuki, [42,43] and FeCl 3 -mediated oxidative [44,45] polymerizations. These reactions are successful when the active species tolerates the presence of water.Reports of aqueous palladium-catalyzed DArP are scarce. [9,46,47] DArP also requires a carbonate base and carboxylic acid additive. Compared to water, carbonate bases display higher Lewis basicities, while carboxylic acids are more acidic. Palladium species preserve the reactivity in the presence of carbonates and carboxylic acids, making them tolerant to water. This study examines the aqueous palladium-catalyzed DArP of 2-bromothiophene derivatives, T1 and T2. The initially selected ligand, triphenylphosphine-3,3′,3″-trisulfonic acid trisodium salt (m-TPPTs), was functional in the DArP; however, its separation from the resultant polymers by dialysis was challenging due to its strong aggregation in water and N,N-dimethylacetamide (DMAc). This was supported by dynamic light scattering (DLS), X-ray crystallography, and gel permeation chromatography (GPC). Thus, pyrimidine-Pd(OAc) 2 was employed in the DArP of T1 to afford PT1 with no ligand (pyrimidine) contamination. Density functional theory (DFT) binding energy calculations revealed that the coordinating ability to palladium was of the order carboxylate > pivalic acid (PivOH) > water, rationalizing the feasibility of executing DArP in water. Finally, the polyelectrolyte molecular-weight overestimation by GPC in water was attributed to the polyelectrolyte effect. Experimental results indicated that the conjugated polyelectrolytes aggregate in DMAc to form a folding structure with the polar groups pointing outwards and conjugated moieties directed inwards, corresponding to a reduced hydrodynamic volume. The polyelectrolyte molecular weight and dispersity (Đ) values determined by GPC in DMAc were, therefore, questionable.

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Section: Methodsmentioning

confidence: 99%

Aqueous Palladium‐Catalyzed Direct Arylation Polymerization of 2‐Bromothiophene Derivatives

Lin

Sun

Yang

et al. 2020

Macromol. Rapid Commun.

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“…Surprisingly, no detailed studies of this phenomenon have been reported that makes following each piece of this puzzle in the literature very difficult. This is even more remarkable as in the area of CH functionalization (Scheme 26), many CH‐activation processes at aliphatic C(sp 3 )‐ or C(sp 2 )‐carbons with C–C or C–X bond formation have been described recently …”

Section: Aliphatic C(sp3)‐h Hydrogen Isotope Exchange Reactionsmentioning

confidence: 95%

Highlights of aliphatic C(sp³)‐H hydrogen isotope exchange reactions

Valero

Derdau

2019

Labelled Comp Radiopharmac

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“…Transition-metal-catalysed direct functionalization of C–H bonds is emerging as one of the most important tools for carbon–carbon bond formation [ 107 , 108 , 109 , 110 , 111 , 112 ]. In particular, direct alkenylation of an inert vinylic C−H bond is particularly attractive for constructing the 1,3-diene moiety, as alkenes are naturally abundant an readily available [ 113 ].…”

Section: Transition Metal-catalysed Cross-coupling Reactionsmentioning

confidence: 99%

Modern Synthetic Methods for the Stereoselective Construction of 1,3-Dienes

Soengas

Rodríguez‐Solla

2021

Molecules

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The 1,3-butadiene motif is widely found in many natural products and drug candidates with relevant biological activities. Moreover, dienes are important targets for synthetic chemists, due to their ability to give access to a wide range of functional group transformations, including a broad range of C-C bond-forming processes. Therefore, the stereoselective preparation of dienes have attracted much attention over the past decades, and the search for new synthetic protocols continues unabated. The aim of this review is to give an overview of the diverse methodologies that have emerged in the last decade, with a focus on the synthetic processes that meet the requirements of efficiency and sustainability of modern organic chemistry.

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Transition metal catalyzed C-H activation for the synthesis of medicinally relevant molecules: A Review

Cited by 56 publications

References 55 publications

Aqueous Palladium‐Catalyzed Direct Arylation Polymerization of 2‐Bromothiophene Derivatives

Aqueous Palladium‐Catalyzed Direct Arylation Polymerization of 2‐Bromothiophene Derivatives

Highlights of aliphatic C(sp³)‐H hydrogen isotope exchange reactions

Modern Synthetic Methods for the Stereoselective Construction of 1,3-Dienes

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Transition metal catalyzed C-H activation for the synthesis of medicinally relevant molecules: A Review

Cited by 56 publications

References 55 publications

Aqueous Palladium‐Catalyzed Direct Arylation Polymerization of 2‐Bromothiophene Derivatives

Aqueous Palladium‐Catalyzed Direct Arylation Polymerization of 2‐Bromothiophene Derivatives

Highlights of aliphatic C(sp3)‐H hydrogen isotope exchange reactions

Modern Synthetic Methods for the Stereoselective Construction of 1,3-Dienes

Contact Info

Product

Resources

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Highlights of aliphatic C(sp³)‐H hydrogen isotope exchange reactions