Versatile halogenation via a CNHC^Csp3 palladacycle intermediate

Teng, Qiaoqiao; Liu, Ziwei; Song, Haobin; Liu, Jiayu; Zhao, Yu; Jiang, Weihua; Huynh, Han Vinh; Meng, Qing

doi:10.1039/d3dt00113j

Cited by 3 publications

(4 citation statements)

References 41 publications

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“…Hypothetically, the original chelation of the C sp2 ^N donor made the palladium electron rich, allowing oxidative addition with Br 2 , reductive elimination of possible Pd (IV) species followed, affording complex 7. 15 This reaction sequence somewhat corroborated the catalytic mechanism of ortho-bromination of aryl-amines with palladium catalysts. 16 Monodentate complex 7 could undergo similar deprotonation with AgOAc to afford the target bidentate complex 8 (Scheme 1, path C).…”

Section: Mitochondrial Membrane Potentialsupporting

confidence: 58%

“…Having obtained the C^N chelate complexes, template‐directed halogenation was attempted with complex 4 , and a brominated version of N‐methyl benzylamine coordinated monodentate complex 7 was isolated. Hypothetically, the original chelation of the C sp2 ^N donor made the palladium electron rich, allowing oxidative addition with Br 2 , reductive elimination of possible Pd (IV) species followed, affording complex 7 15 . This reaction sequence somewhat corroborated the catalytic mechanism of ortho‐bromination of aryl‐amines with palladium catalysts 16 .…”

Section: Resultsmentioning

confidence: 59%

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Mixed N‐heterocyclic carbene and benzyl‐, phenethyl‐, and biphenylamine coordinated Pd complexes: Anticancer activities and stereo‐electronic effects

Teng,

Song,

Chen

et al. 2024

Applied Organom Chemis

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A series of mixed N‐heterocylic carbene (NHC) palladium complexes bearing C^N bidentate ligands derived from benzylamine, phenethylamine, and biphenylamine were prepared and fully characterized by NMR spectroscopy, ESI‐MS spectrometry, and X‐ray diffraction analyses. The complexes were potent in inhibiting proliferation of HepG2 and Caco2 cancer cells, and a SAR (structure–activity relationship) study revealed C^N ligands with stronger electron donation and moderate steric hindrance are more cytotoxic. DNA binding study through UV–vis absorption titration indicated that such complexes bound stronger to CT‐DNA molecules with higher binding constants. Additional molecular docking of the best performer suggested a groove binding mode through hydrogen bonding and π‐π stacking interactions. The apoptosis induced by the two best performers of α,α‐dimethylbenzylamine and S‐α‐methylbenzylamine ligated complexes was further analyzed by morphology change, cell cycle distribution, ROS production, and mitochondrial membrane potential studies.

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Section: Mitochondrial Membrane Potentialsupporting

confidence: 58%

Section: Resultsmentioning

confidence: 59%

Mixed N‐heterocyclic carbene and benzyl‐, phenethyl‐, and biphenylamine coordinated Pd complexes: Anticancer activities and stereo‐electronic effects

Teng,

Song,

Chen

et al. 2024

Applied Organom Chemis

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“…13 C{1H} NMR (75.47 MHz, CDCl 3 ): δ 167.2 5 (NCN), 162.8 (q, 2 J(C,F) = 34.9 Hz, CO 2 ), 133.2, 124.8, 113.7 (Ar−C), 120.6 (q, 1 J(C,F) = 289 Hz, CF 3 ), 55.2 (NCH), 22.5 (CH 3 ). 19 F NMR (282 MHz, CDCl 3 ): δ 1.84 (s, CF 3 ). Anal.…”

Section: 3-diisopropylbenzimidazolin-2-ylidene(nitrato)gold(i) (2)mentioning

confidence: 99%

“…In contribution to this area, we have developed an alternative methodology for the evaluation and comparison of donor strengths that is simple and can be applied across many different ligand families. , Using palladium NHC complexes of the type trans -[PdBr 2 ( i Pr 2 -bimy)L], [PdBr( i Pr 2 -bimy)(L^L)] + , [PdBr( i Pr 2 -bimy)(L^L′)] + and [PdBr( i Pr 2 -bimy)(L^X)], monodentate (HEP, L) , as well as bidentate ligands (HEP2: L^L, L^L′, L^X) − can be probed with the Huynh Electronic Parameter (HEP) by comparing the 13 C carbene NMR signals (HEP/HEP2 values) of the i Pr 2 -bimy (1,3-diisopropyl-benzimidazolin-2-ylidene) reporter ligand.…”

Section: Introductionmentioning

confidence: 99%

Donor Strength Determination of Anionic Ligands

Huynh,

Leung,

Lam

2023

Inorg. Chem.

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14 new gold(I) NHC complexes of the type [AuX( i Pr 2 -bimy)] ( i Pr 2 -bimy = 1,3-diisopropylbenzimidazolin-2ylidene) have been prepared and fully characterized. These complexes and their reported analogues were used to systematically compare and rank the donating abilities of overall 34 anionic Xtype donors by 13 C NMR spectroscopy. Specifically, the carbene chemical shift of the i Pr 2 -bimy ligand was found to be responsive to the ligand X spanning an overall range Δδ > 37 ppm between the strongest and weakest donor in this study.

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Palladium‐Catalyzed C(sp³)−H Activation in A Monoterpene‐Based Compound Under Mild Conditions: A Combined Experimental and Theoretical Mechanistic Study

Kokina,

Shekhovtsov,

Tkachev

et al. 2024

ChemPlusChem

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The first example of the palladium‐catalyzed sp3 C‐H bond activation in a monoterpene‐based compound has been observed in the reaction of PdCl2 with a (+)‐3‐carene‐based ligand HL (HL = N‐((1aS,3S,7bR)‐1,1,3‐trimethyl‐7‐phenyl‐5‐(pyridin‐2‐yl)‐1a,2,3,7b‐tetrahydro‐1H‐cyclopropa[f]quinolin‐3‐yl)acetamide), which yielded the [PdLCl] complex. In contrast to the vast majority of C(sp3)‐H activation reactions which require prolonged heating and mixing due to the inert character of the corresponding bond, the reaction reported herein proceeds rapidly under mild conditions. A theoretical insight into the ligand deprotonation has been performed by DFT calculations. The mechanism of the C‐H activation involves (i) simultaneous coordination of the CH3 group of HL to the Pd2+ ion and decoordination of the Cl‐ anion with consequent formation of a Cl⋅⋅⋅H‐N hydrogen bond with the amide group, (ii) approximation of the out‐of‐sphere Cl‐ anion to one of the hydrogen atoms of the CH3 group mediated by the crane motion of the amide group and (iii) the ejection of the HCl molecule, which increases the entropy of the system and serves as a driving force for the reaction.

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Versatile halogenation via a C_NHC^C_sp3 palladacycle intermediate

Abstract: Stable cyclopalladated complexes containing an (sp3)C–Pd bond were synthesized via α-CH2 deprotonation and palladation of N-alkyl groups of carbene ligands bearing electron-withdrawing substitutents. Strong electron donating strengths of the resulting...

Cited by 3 publications

References 41 publications

Mixed N‐heterocyclic carbene and benzyl‐, phenethyl‐, and biphenylamine coordinated Pd complexes: Anticancer activities and stereo‐electronic effects

Mixed N‐heterocyclic carbene and benzyl‐, phenethyl‐, and biphenylamine coordinated Pd complexes: Anticancer activities and stereo‐electronic effects

Donor Strength Determination of Anionic Ligands

Palladium‐Catalyzed C(sp³)−H Activation in A Monoterpene‐Based Compound Under Mild Conditions: A Combined Experimental and Theoretical Mechanistic Study

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Versatile halogenation via a CNHC^Csp3 palladacycle intermediate

Abstract: Stable cyclopalladated complexes containing an (sp3)C–Pd bond were synthesized via α-CH2 deprotonation and palladation of N-alkyl groups of carbene ligands bearing electron-withdrawing substitutents. Strong electron donating strengths of the resulting...

Cited by 3 publications

References 41 publications

Mixed N‐heterocyclic carbene and benzyl‐, phenethyl‐, and biphenylamine coordinated Pd complexes: Anticancer activities and stereo‐electronic effects

Mixed N‐heterocyclic carbene and benzyl‐, phenethyl‐, and biphenylamine coordinated Pd complexes: Anticancer activities and stereo‐electronic effects

Donor Strength Determination of Anionic Ligands

Palladium‐Catalyzed C(sp3)−H Activation in A Monoterpene‐Based Compound Under Mild Conditions: A Combined Experimental and Theoretical Mechanistic Study

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Product

Resources

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Versatile halogenation via a C_NHC^C_sp3 palladacycle intermediate

Palladium‐Catalyzed C(sp³)−H Activation in A Monoterpene‐Based Compound Under Mild Conditions: A Combined Experimental and Theoretical Mechanistic Study