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41.
Daly SR Klaehn JR Boland KS Kozimor SA MacInnes MM Peterman DR Scott BL 《Dalton transactions (Cambridge, England : 2003)》2012,41(7):2163-2175
Synthetic routes to alkyl and aryl substituted dithiophosphinate salts that contain non-coordinating PPh(4)(+) counter cations are reported. In general, these compounds can be prepared via a multi-step procedure that starts with reacting secondary phosphines, i.e. HPR(2), with two equivalents of elemental S. The synthetic transformation proceeds by oxidation of the phosphine followed by insertion of S into the H-P bond. This approach was used to synthesize a series of dithiophosphinic acids that were fully characterized, namely HS(2)P(p-CF(3)C(6)H(4))(2), HS(2)P(m-CF(3)C(6)H(4))(2), HS(2)P(o-MeC(6)H(4))(2) and HS(2)P(o-MeOC(6)H(4))(2). Although the insertion step was found to be much slower than the oxidation reaction, the formation of (NH(4))S(2)PR(2) from HPSR(2) occurred rapidly upon addition of NH(4)OH. Subsequent cation exchange reactions proceeded readily with PPh(4)Cl in water, under air and at ambient conditions to provide analytically pure samples of [PPh(4)][S(2)PR(2)] (R = p-CF(3)C(6)H(4), m-CF(3)C(6)H(4), o-CF(3)C(6)H(4), o-MeC(6)H(4), o-MeOC(6)H(4), Ph, and Me, 1b-7b, respectively), which were characterized by elemental analysis, multinuclear NMR, and IR spectroscopy. In addition, S(2)PPh(2)(-) and dithiophosphinates with ortho-substituted aryl groups (3b-6b) were characterized by X-ray crystallography. As opposed to the acids, which have short P=S double bonds and long P-SH single bonds, the metric parameters for the S atoms in S(2)PR(2)(-) are equivalent. In addition, the presence of large non-coordinating PPh(4)(+) cations guard against intermolecular P-S···X interactions and ensure that the P-S bond is isolated. These S(2)PR(2)(-) anions, which can be prepared in large quantities and isolated in crystalline form, are attractive for spectroscopic and theoretical studies because the P-S interaction can be probed independently in the absence of intermolecular interactions. 相似文献
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Rynne A. Hankins Molly E. Carter Changlei Zhu Chen Chen John C. Lukesh III 《Chemical science》2022,13(44):13094
Like hydrogen sulfide (H2S), its chalcogen congener, hydrogen selenide (H2Se), is an emerging molecule of interest given its endogenous expression and purported biological activity. However, unlike H2S, detailed investigations into the chemical biology of H2Se are limited and little is known about its innate physiological functions, cellular targets, and therapeutic potential. The obscurity surrounding these fundamental questions is largely due to a lack of small molecule donors that can effectively increase the bioavailability of H2Se through their continuous liberation of the transient biomolecule under physiologically relevant conditions. Driven by this unmet demand for H2Se-releasing moieties, we report that γ-keto selenides provide a useful platform for H2Se donation via an α-deprotonation/β-elimination pathway that is highly dependent on both pH and alpha proton acidity. These attributes afforded a small library of donors with highly variable rates of release (higher alpha proton acidity = faster selenide liberation), which is accelerated under neutral to slightly basic conditions—a feature that is unique and complimentary to previously reported H2Se donors. We also demonstrate the impressive anticancer activity of γ-keto selenides in both HeLa and HCT116 cells in culture, which is likely to stimulate additional interest and research into the biological activity and anticancer effects of H2Se. Collectively, these results indicate that γ-keto selenides provide a highly versatile and effective framework for H2Se donation.Like hydrogen sulfide (H2S), its chalcogen congener, hydrogen selenide (H2Se), is an emerging biomolecule of interest. Therefore, small molecule donors that effectively increase its bioavailability are desired to further probe H2Se chemical biology. 相似文献
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Joel A. Tickner Rachel V. Simon Molly Jacobs Lindsey D. Pollard Saskia K. van Bergen 《Green Chemistry Letters and Reviews》2021,14(1):21-42
ABSTRACT Alternatives assessment and green chemistry share a common goal of supporting the transition to safer, more sustainable chemicals, materials, and products. Yet the two fields, and their respective scientific communities, are not well integrated. To better understand the nexus between alternatives assessment and green chemistry as complementary approaches to support the development and adoption of safer, more sustainable chemicals for specific functional uses, this article discusses the foundations of the two fields and examines two case examples in which companies have utilized the tools and approaches of both disciplines in developing safer chemical solutions. This research demonstrates the importance and utility of the overlapping skillsets and tools of the two disciplines and the potential benefit of educational opportunities and collaborative spaces in jointly strengthening both fields. Additionally, the literature and case examples identify a number of research and practice needs that would bolster the application of both alternatives assessment and green chemistry in supporting the transition to safer, more sustainable chemistry, including: clearer definitions and criteria of what is ‘safer’; improved approaches to evaluate potential unintended consequences of chemical applications; and more effective tools to evaluate toxicity, consider inherent exposure trade-offs, and combine multiple attributes to make an informed decision. 相似文献
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Brooke A. Versaw Molly E. McFadden Corey C. Husic Maxwell J. Robb 《Chemical science》2020,11(17):4525
Mechanochromic molecular force probes conveniently report on stress and strain in polymeric materials through straightforward visual cues. We capitalize on the versatility of the naphthopyran framework to design a series of mechanochromic mechanophores that exhibit highly tunable color and fading kinetics after mechanochemical activation. Structurally diverse naphthopyran crosslinkers are synthesized and covalently incorporated into silicone elastomers, where the mechanochemical ring–opening reactions are achieved under tension to generate the merocyanine dyes. Strategic structural modifications to the naphthopyran mechanophore scaffold produce dramatic differences in the color and thermal electrocyclization behavior of the corresponding merocyanine dyes. The color of the merocyanines varies from orange-yellow to purple upon the introduction of an electron donating pyrrolidine substituent, while the rate of thermal electrocyclization is controlled through electronic and steric factors, enabling access to derivatives that display both fast-fading and persistent coloration after mechanical activation and subsequent stress relaxation. In addition to identifying key structure–property relationships for tuning the behavior of the naphthopyran mechanophore, the modularity of the naphthopyran platform is demonstrated by leveraging blends of structurally distinct mechanophores to create materials with desirable multicolor mechanochromic and complex stimuli-responsive behavior, expanding the scope and accessibility of force-responsive materials for applications such as multimodal sensing.Structure–activity relationships for strategic substitution of the naphthopyran mechanophore scaffold enable polymeric materials with tunable mechanochromic behavior. 相似文献
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Molly E Hoke Marc-Raleigh Brescia Suzanne Bogaczyk Philip DeShong Bryan W King Michael T Crimmins 《The Journal of organic chemistry》2002,67(2):327-335
The regioselectivity of Pd-catalyzed malonate additions and arylations to cycloalkenyl esters can be predicted by completing a stereochemical analysis of the Pd-pi-allyl complex. The Pd-catalyzed malonate additions which have the greatest degree of regioselectivity are in which substituents have a steric influence in blocking the incoming nucleophile. Cyclopentenyl substrates displayed lower regioselectivity than the cyclohexyl counterparts presumably due to increased planarity of the system. Arylations using tin and hypervalent silicon reagents were compared. 相似文献