Electrochemical Reduction in an Aprotic Medium of New Functionalized Amphiphilic Molecules Derived from Sugars: Stereoselective Pinacolization and an Example of a Glycosidic Carbon-Oxygen Bond Cleavage

Maurice, Catherine; Schöllhorn, Bernd; Canet, Isabelle; Mousset, G.; Mousty, Christine; Guilbot, Jérôme; Plusquellec, Daniel

doi:10.1002/(sici)1099-0690(200003)2000:5<813::aid-ejoc813>3.0.co;2-q

Cited by 7 publications

(5 citation statements)

References 19 publications

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“…Although an increased basicity of the amino group 34 appears to correlate with a small anodic shift of the Fe II /Fe III oxidation peak (Table 2), there is no significant effect as expected from the remoteness of the tertiary amine in relation to the metal center. The irreversible cathodic wave (II) can be attributed to redox processes occurring within the acyl benzo [b]thiophene moiety, such as the reduction of the carbonyl group 35 or of the benzo- [b]thiophene skeleton. 36 Anodic oxidation at the tertiary amino group, 37 though also conceivable for compounds 9-13, was not detected in our experiments.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of New Organometallic Benzo[b]thiophene Derivatives with Potential Antitumor Properties

Ferreira¹,

Silva²,

Duarte³

et al. 2009

Organometallics

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The incorporation of organometallic moieties into the structure of known active drugs to improve their therapeutic properties has gained considerable interest in recent years. The benzo- [b]thiophene derivative raloxifene is a selective estrogen receptor modulator (SERM) that has been found to decrease breast cancer risk in postmenopausal women compared to placebo. The current data suggest that, in the postmenopausal setting, raloxifene may have the benefits of the widely used tamoxifen with fewer side effects. As part of a program designed toward the synthesis and biological screening of organometallic benzo[b]thiophene derivatives inspired by the structure of raloxifene, we have prepared a series of 2-benzoyl-3-ferrocenylbenzo[b]thiophenes where the benzoyl sub- stituent contains terminal tertiary alkylamino groups, expected to ensure affinity to the estrogen receptor. The synthetic strategy and full characterization (NMR, MS, X-ray diffraction, cyclic voltammetry) of the new ferrocenylbenzo[b]thiophenes is reported herein. Moreover, the new 2- benzoyl-3-ferrocenylbenzo[b]thiophene derivatives were tested for their cytotoxic properties against several human tumor cell lines. All the test compounds showed considerable cytotoxic activity; among these, [3-ferrocenyl-6-methoxybenzo[b]thiophen-2-yl][4-(piperazin-1-yl)methyl- phenyl]methanone (compound 13) is of note, showing IC50 values in the low-micromolar range and more than 1 order of magnitude lower than those of the reference compound, cisplatin. In addition, chemosensitivity tests on resistant phenotypes indicated that compound 13 elicited no cross-resistance with cisplatin, besides not being a potential multidrug-resistant (MDR) substrate. Moreover, caspase-3 activation analyses revealed that 13 induced a caspase-3-dependent apoptotic cell-death mechanism. Taken together, these data suggest that the new 2-benzoyl-3- ferrocenylbenzo[b]thiophenes, in particular compound 13, have potentially useful antitumor properties

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Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of New Organometallic Benzo[b]thiophene Derivatives with Potential Antitumor Properties

Ferreira¹,

Silva²,

Duarte³

et al. 2009

Organometallics

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“…Electrochemical pinacol coupling would be a promising alternative to avoid the use of low-valent metal reductants. The reported methods commonly carried out in a divided cell [29][30][31][32][33][34] or an undivided cell with sacrificial anodes [35], such as Al, Mg, and Sn, to prevent undesired oxidative reactions (Scheme 1b) [36][37][38][39]. While sacrificial anodes enable the reactions to be performed with a simple and user-friendly undivided cell set-up, consuming the anode material with generating stoichiometric metal waste may be a serious issue in terms of green and sustainable chemistry.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical formal homocoupling of sec-alcohols

Yamamoto¹,

Arita²,

Shiota³

et al. 2022

Beilstein J. Org. Chem.

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Electrochemical pinacol coupling of carbonyl compounds in an undivided cell with a sacrificial anode would be a promising approach toward synthetically valuable vic-1,2-diol scaffolds without using low-valent metal reductants. However, sacrificial anodes produce an equimolar amount of metal waste, which may be a major issue in terms of sustainable chemistry. Herein, we report a sacrificial anode-free electrochemical protocol for the synthesis of pinacol-type vic-1,2-diols from sec-alcohols, namely benzyl alcohol derivatives and ethyl lactate. The corresponding vic-1,2-diols are obtained in moderate to good yields, and good to high levels of stereoselectivity are observed for sec-benzyl alcohol derivatives. The present transformations smoothly proceed in a simple undivided cell under constant current conditions without the use of external chemical oxidants/reductants, and transition-metal catalysts.

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“…It is found the dl/meso rato of hydrodimer can vary from 0.3-19. Proton is a key factor, it is implied that aprotic environment favors the formation of dl-hydrodimer (Bewick and Brown, 1977;Bewick and Cleghorn, 1973;Smith and Utley, 1981;Stocker and Jenevein, 1968b;Maurice et al, 2000). It has been shown that the stereo-selectivity can also be influenced by ionic liquids.…”

Section: Introductionmentioning

confidence: 99%

The Application of Ionic Liquids in Catholic Coupling of Acetophenone

Cheng¹

2010

Energy Research J.

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Problem statement: The cathodic coupling of acetophnone was carried out in aqueous solutions containing sodium sulfate and 1-Octyl-3-Methylimidazolium Chloride ([OMIM]Cl) as supporting electrolytes. [OMIM]Cl is an ionic liquid, also serving as a co-solvent to prevent the deposition of products during electrolysis. The products are extracted with ether after electrolyses. Approach: It is shown in this study that the recycling of the aqueous Na 2 SO 4-[OMIM]Cl electrolytes is feasible. Results: The new electrolytic process is more energy saving and environment-friendly than conventional ones. Conclusion: On the other hand, the ratios of dl-to meso pinacols formed in the electrochemical reduction of acetophenone can be more than 9, higher than ever reported for any aqueous system.

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Electrochemical Reduction in an Aprotic Medium of New Functionalized Amphiphilic Molecules Derived from Sugars: Stereoselective Pinacolization and an Example of a Glycosidic Carbon-Oxygen Bond Cleavage

Cited by 7 publications

References 19 publications

Synthesis and Characterization of New Organometallic Benzo[b]thiophene Derivatives with Potential Antitumor Properties

Synthesis and Characterization of New Organometallic Benzo[b]thiophene Derivatives with Potential Antitumor Properties

Electrochemical formal homocoupling of sec-alcohols

The Application of Ionic Liquids in Catholic Coupling of Acetophenone

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