Tandem α/β-alkylation and transfer hydrogenation by heterodimetallic ruthenium-iridium complex

Dehury, Niranjan; Mishra, Saumya Ranjan; Laha, Paltan; Patra, Srikanta

doi:10.1016/j.ica.2020.119796

Cited by 6 publications

(2 citation statements)

References 67 publications

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“…The development of transition metal-based multimetallic systems with suitable ligand frameworks is a fascinating area of contemporary research. Such systems often display new/improved properties against their monometallic analogues and find diverse applications in chemistry and biology. − Recently, the exploration of such systems as anticancer agents − has gained serious momentum with the success of their mononuclear analogues. In addition, they have demonstrated a significant improvement in anticancer activity and exhibit a different mechanism of cell death compared to cisplatin. , …”

Section: Introductionmentioning

confidence: 99%

Asymmetrically Coordinated Heterodimetallic Ir–Ru System: Synthesis, Computational, and Anticancer Aspects

et al. 2023

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Herein, we present an unprecedented formation of a heterodinuclear complex [{(ppy)2IrIII}(μ-phpy){RuII(tpy)}](ClO4)2 {[1](ClO4)2} using terpyridyl/phenylpyridine as ancillary ligands and asymmetric phpy as a bridging ligand. The asymmetric binding mode (N∧N-∩-N∧N∧C–) of the phpy ligand in {[1](ClO4)2} is confirmed by 1H, 13C, 1H–1H correlated spectroscopy (COSY), high-resolution mass spectrum (HRMS), single-crystal X-ray crystallography techniques, and solution conductivity measurements. Theoretical investigation suggests that the highest occupied molecular orbital (HOMO) and the least unoccupied molecular orbital (LUMO) of [1]2+ are located on iridium/ppy and phpy, respectively. The complex displays a broad low energy charge transfer (CT) band within 450–575 nm. The time-dependent density functional theory (TDDFT) analysis suggests this as a mixture of metal-to-ligand charge transfer (MLCT) and ligand-to-ligand charge transfer (LLCT), where both ruthenium, iridium, and ligands are involved. Complex {[1](ClO4)2} exhibits RuIIIrIII/RuIIIIrIII- and RuIIIIrIII/RuIIIIrIV-based oxidative couples at 0.83 and 1.39 V, respectively. The complex shows anticancer activity and selectivity toward human breast cancer cells (IC50; MCF-7: 9.3 ± 1.2 μM, and MDA-MB-231: 8.6 ± 1.2 μM) over normal breast cells (MCF 10A: IC50 ≈ 21 ± 1.3 μM). The Western blot analysis and fluorescence microscopy images suggest that combined apoptosis and autophagy are responsible for cancer cell death.

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Section: Introductionmentioning

confidence: 99%

Asymmetrically Coordinated Heterodimetallic Ir–Ru System: Synthesis, Computational, and Anticancer Aspects

et al. 2023

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“…For example, the cross‐coupling of alcohols was realized with Mn, [9] Cu, [10] Ru, [11] Ni, [12] Co, [13] Zr, [14] Rh, [15] Pd, [16] Au [17] catalysts. In addition to single metal‐catalyzed coupling, the mixed metal catalysts, such as Cu−Ag, [18] Pt−Sn, [19] Ag−Al, [20] Ru‐Ir [21] were also reported.…”

Section: Introductionmentioning

confidence: 99%

Iridium Complexes as Efficient Catalysts for Construction of α‐Substituted Ketones via Hydrogen Borrowing of Alcohols in Water

et al. 2021

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Ketones are of great importance in synthesis, biology, and pharmaceuticals. This paper reports an iridium complexes‐catalyzed cross‐coupling of alcohols via hydrogen borrowing, affording a series of α‐alkylated ketones in high yield (86 %–95 %) and chemoselectivities (>99 : 1). This methodology has the advantages of low catalyst loading (0.1 mol%) and environmentally benign water as the solvent. Studies have shown the amount of base has a great impact on chemoselectivities. Meanwhile, deuteration experiments show water plays an important role in accelerating the reduction of the unsaturated ketones intermediates. Remarkably, a gram‐scale experiment demonstrates this methodology of iridium‐catalyzed cross‐coupling of alcohols has potential application in the practical synthesis of α‐alkylated ketones.

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Ru‐Catalyzed CC Bond Formation Through Alcohol Dehydrogenative Coupling Strategy

Panja¹,

Ganguli²,

Kundu³

2022

Handbook of CH-Functionalization

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Finding a greener and more sustainable alternative to the waste generating conventional protocols for the synthesis of CC bonds is a challenging goal in current chemical research. In this context, utilization of alcohol dehydrogenative coupling strategy has gained significant importance as it uses bio‐mass derived alcohols as the reagent and produces water as the by‐product. In this article, following the borrowing hydrogen (BH) and acceptorless dehydrogenative coupling (ADC) strategy, the progress and the improvements of the Ru‐based catalytic systems using various bidentate and tridentate ligands with diverse electronic and steric compatibilities for the CC bond formation are summarized. Following these protocols, synthesis of several alkylated ketones, alcohols, nitriles, amides, and indoles was successfully executed. Utilizing alcohols, development of these Ru‐catalyzed atom‐economical, sustainable, and efficient CC bond formation protocols becomes one of the essential tools in organic chemistry to synthesize numerous value‐added products.

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Tandem α/β-alkylation and transfer hydrogenation by heterodimetallic ruthenium-iridium complex

Cited by 6 publications

References 67 publications

Asymmetrically Coordinated Heterodimetallic Ir–Ru System: Synthesis, Computational, and Anticancer Aspects

Asymmetrically Coordinated Heterodimetallic Ir–Ru System: Synthesis, Computational, and Anticancer Aspects

Iridium Complexes as Efficient Catalysts for Construction of α‐Substituted Ketones via Hydrogen Borrowing of Alcohols in Water

Ru‐Catalyzed CC Bond Formation Through Alcohol Dehydrogenative Coupling Strategy

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