Synthesis and anodic electrochemistry of cymanquine and related complexes

Lam, Kevin; Geiger, William E.

doi:10.1016/j.jorganchem.2016.05.009

Cited by 10 publications

(5 citation statements)

References 47 publications

(48 reference statements)

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“…[38] At an appropriate time in the experiment, [NBu 4 ][B(C 6 F 5 ) 4 ]w as prepared as previously described. [39] X-ray crystallography. Experimental intensities were measured on aS TADIVARI Pilatus (for 5 and 6)d iffractometer using the w-scan mode.…”

Section: Methodsmentioning

confidence: 99%

Molecular Oligogermanes and Related Compounds: Structure, Optical and Semiconductor Properties

Zaitsev

Тафеенко

Oprunenko

et al. 2017

Chemistry An Asian Journal

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Section: Methodsmentioning

confidence: 99%

Molecular Oligogermanes and Related Compounds: Structure, Optical and Semiconductor Properties

Zaitsev

Тафеенко

Oprunenko

et al. 2017

Chemistry An Asian Journal

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“…Cymanquine (compound 4, Figure 1), pseudocymanquine (compound 5, Figure 1) and ferroquine (compound 3, Figure 1) were synthesized as previously described. 19,21 A complete description of the synthesis of O-pseudocymanquine (pCMQ-O, compound 6, Figure 1) can be found in Supplementary Information.…”

Section: Synthesis Of Compoundsmentioning

confidence: 99%

“…We characterize the anticancer activity of a newly described organometallic CQ derivative called Cymanquine (CMQ) . CMQ is a CQ derivative containing a cymantrene substitution that leads to greater cytotoxic activity in vitro to tumor cells compared to traditional quinolines, in both low and normal pH environments.…”

Section: Introductionmentioning

confidence: 99%

“…18 We characterize the anticancer activity of a newly described organometallic CQ derivative called Cymanquine (CMQ). 19,20 CMQ is a CQ derivative containing a cymantrene substitution that leads to greater cytotoxic activity in vitro to tumor cells compared to traditional quinolines, in both low and normal pH environments. The apparent mechanism for cytotoxicity is supported by data showing increased lysosomal accumulation and disruption of lysosome-dependent autophagy.…”

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confidence: 99%

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Novel organometallic chloroquine derivative inhibits tumor growth

Hall

Ramsey

Peng

et al. 2018

J of Cellular Biochemistry

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Autophagy has emerged as a mechanism critical to both tumorigenesis and development of resistance to multiple lines of anti-cancer therapy. Therefore, targeting autophagy and alternative cell death pathways has arisen as a viable strategy for refractory tumors. The anti-malarial 4-aminoquinoline compounds chloroquine and hydroxychloroquine are currently being considered for re-purposing as anti-cancer therapies intended to sensitize different tumors by targeting the lysosomal cell death pathway. Here, we describe a novel organometallic chloroquine derivative, cymanquine, that exhibits enhanced bioactivity compared to chloroquine in both normal, and reduced pH tumor microenvironments, thus overcoming a defined limitation of traditional 4-aminoquinolines. In vitro, cymanquine exhibits greater potency than CQ in a diverse panel of human cancer cell lines, including melanoma, in both normal pH and in reduced pH conditions that mimic the tumor microenvironment. Cymanquine treatment results in greater lysosomal accumulation than chloroquine and induces lysosomal dysfunction leading to autophagy blockade. Using a mouse model of vemurafenib-resistant melanoma, cymanquine slowed tumor growth greater than hydroxychloroquine, and when used in combination with vemurafenib, cymanquine partially restored sensitivity to vemurafenib. Overall, we show that cymanquine exhibits superior lysosomal accumulation and autophagy blockade than either chloroquine or hydroxychloroquine in vitro; and in addition to its high level of tolerability in mice, exhibits superior in vivo efficacy in a model of human melanoma.

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“…The metal carbonyl complex that is arguably most confluent with ferrocene is the half-sandwich piano-stool complex cyclopentadienylmanganese tricarbonyl, MnCp(CO) 3 (“cymantrene”) . Although this unit and its rhenium analogue have been employed as molecular tags in bioorganometallic chemistry, − the oxidative (anodic) electrochemistry of the tagged systems has generally not been reported. As discussed elsewhere, owing to the fact that cymantrene and ferrocene are both pseudo-octahedral, first-row, d 6 metal complexes, they share certain similarities in electronic properties, especially among their highest energy filled orbitals.…”

Section: Introductionmentioning

confidence: 99%

Oxidation of Cymantrene-Tagged Tamoxifen Analogues: Effect of Diphenyl Functionalization on the Redox Mechanism

Pudasaini

Park

et al. 2020

Organometallics

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The oxidations of 1,1′-di-p-anisolyl-2-cymantrenylbutene (3b) and 1,1′-di-p-hydroxyphenyl-2-cymantrenylbutene (3c) were investigated by electrochemical and spectroscopic experiments and by density functional theory (DFT) calculations. Both compounds undergo a reversible one-electron oxidation followed closely by a partially chemically reversible second oxidation (E 1/2 values vs ferrocene: 0.60 and 0.74 V for 3b; 0.63 and 0.78 V for 3c). In comparison to the nonphenyl-functionalized parent, 1,1′diphenyl-2-cymantrenylbutene (3a), 3b,c have lower and more closely spaced oxidation potentials and more rapid follow-up reactions of their dications, 3b 2+ and 3c 2+ . Shifts in the calculated charge distributions of the neutral compounds and their singly and doubly oxidized products corroborated trends in the measured shifts of Mn−CO ν CO frequencies in assigning the redox sites primarily to the diarylbutene fragment. Upon removal of electrons, the lost charge density is partially compensated by the polarizable cymantrenyl tag. The half-lives of the dications 3b 2+ and 3c 2+ are about 10 s at room temperature in dichloromethane/0.05 M [NBu 4 ][B(C 6 F 5 ) 4 ]. Their follow-up reactions are initiated by loss of a proton either from a hydroxyl group or from the CH 2 group of the diarylbutene unit, giving rise to two products having quinone methide structures. Although the initial oxidation sites of cymantrene-tagged diarylbutenes are primarily ligand based and those of ferrocene-tagged diarylbutenes are metalbased, the ultimate oxidation products of their p-OH-or p-OMe-functionalized derivatives are very similar.

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Synthesis and anodic electrochemistry of cymanquine and related complexes

Cited by 10 publications

References 47 publications

Molecular Oligogermanes and Related Compounds: Structure, Optical and Semiconductor Properties

Molecular Oligogermanes and Related Compounds: Structure, Optical and Semiconductor Properties

Novel organometallic chloroquine derivative inhibits tumor growth

Oxidation of Cymantrene-Tagged Tamoxifen Analogues: Effect of Diphenyl Functionalization on the Redox Mechanism

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