Convenient Iterative Synthesis of an Octameric Tetracarboxylate-Functionalized Oligophenylene Rod with Divergent End Groups

Read, Mark W.; Escobedo, Jorge O.; Willis, Douglas M.; Beck, Patricia; Strongin, Robert M.

doi:10.1021/ol000204k

Cited by 47 publications

(18 citation statements)

References 28 publications

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“…Initial attempts to prepare compound 10 involved the synthesis of a bromo-substituted rhodamine,[17] followed by a Suzuki coupling reaction with the corresponding boronic acid. [21] Suzuki coupling afforded complex product mixtures (ESI). An alternative approach using microwave irradiation via direct condensation of 8 and 9 followed by oxidation with p -chloranil successfully afforded 10 in 67 % yield.…”

Section: Resultsmentioning

confidence: 99%

Rhodamine analogs for molecular ruler applications

et al. 2016

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Section: Resultsmentioning

confidence: 99%

Rhodamine analogs for molecular ruler applications

et al. 2016

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“…[8,10] Strongin and coworkers prepared the tetracarboxylatefunctionalized p-phenylene 8-mer 25 8 using an IDC strategy varying from the work of Schlüter and coworkers, [29] by the utilization of an amine group instead of a bromide as precursor of the iodide required for chain length doubling by Suzuki cross-coupling with a complementary aryl boronate derivative (Scheme 10). [30] The starting orthogonally protected dimer 25 2 was obtained in one-step and contained bromo-and amino-protected chain ends. Orthogonal deprotection involved either conversion of the bromide to the boronate by reaction with bis(pinacolato)-diboron and PdCl 2 (dppf) (dppf stands for 1,1-bis(diphenylphosphino)ferrocene), or conversion of the amino group to an iodide in the presence of I 2 /t-BuONO, yielding monoprotected dimers 26 2 and 27 2 , respectively.…”

Section: Oligo(p-phenylene)s (Opps)mentioning

confidence: 99%

Precise Synthesis of Molecularly Defined Oligomers and Polymers by Orthogonal Iterative Divergent/Convergent Approaches

Binauld

Damiron

Connal

et al. 2010

Macromol. Rapid Commun.

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The synthesis of perfectly defined (macro)molecules has been a constant challenge for polymer and organic chemists. This paper highlights the main applications of the iterative divergent/convergent approach for the synthesis of discrete mass oligomers and polymers. We will discuss the orthogonal deprotection and coupling strategies involved in this powerful strategy where chain length doubles at each iteration and which has been applied to the synthesis of conjugated rigid rods as well as amorphous and crystalline oligomers and polymers. The synthesis of perfectly defined oligomers in respect to emerging highly efficient and orthogonal chemistries will also be highlighted.

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“…60 After extensive optimization, the Suzuki coupling reaction of bromo-substituted rhodamine with boronic acid gave precursor 2.19;…”

Section: Scheme 22 Synthesis Of Hydroxyl-quinoline Precursor 217mentioning

confidence: 99%

Custom Fluorophores for Investigating the Cellular Uptake Mechanisms and Side-Effects of Pharmaceuticals

Chu¹

2000

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There is a significant current need to elucidate the molecular mechanisms of the side-effects caused by widely-used pharmaceuticals. Examples include the acute nephrotoxicity and irreversible ototoxicity promoted by the cationic drugs gentamicin and cisplatin. Gentamicin is an aminoglycoside antibiotic used for the prevention and treatment of life-threatening gram-negative bacterial infections, such as tuberculosis and meningitis. Cisplatin is used to treat a broad spectrum of cancers including head and neck, ovarian, cervical, stomach, bladder, sarcoma, lymphoma, testicular cancer and others.The objective of this study is to design and synthesize rhodamine derivatives that can be used for the construction of geometrically well-defined cationic drug conjugates.The long-term goal is to use the conjugates as tools to aid in elucidating the properties and identities of ion channels involved in the uptake of cationic pharmaceuticals into kidney and cochlear hair cells. This will shed light on the origin and potential prevention of unwanted side effects such as nephrotoxicity and ototoxicity associated with specific cationic drugs.A series of extended rhodamine analogs with reactive groups for biomolecule conjugation has been synthesized. These fluorophores show similar spectral properties to their prototype, Texas Red succinimidyl ester (TR-SE). However, they contain rigid linkers between the fluorophore and amine-reactive moiety. The resultant gentamicin conjugates of these materials are rigidified enabling one to assess channel pore dimensions without the confounding issue of conjugate folding. Preliminary cell studies are promising, as one observes reduced gentamicin uptake in both kidney and sensory ii hair cell upon systematically increasing the dimension of the fluorophore. This work has enabled us to tentatively assign the maximum dilated MET channel pore size as between 1.44 nm to 1.56 nm. However, this preliminary finding, though encouraging, needs further validation via ongoing studies with larger diameter fluorophore conjugates, A cisplatin-Texas Red conjugate has also been synthesized to enable studies of cellular uptake mechanisms. This conjugate preserves not only the spectral properties of Texas Red after conjugation, but also the cytotoxicity of cisplatin. This has been validated in zebrafish. The series of rhodamine probes that have been conjugated to gentamicin should be similarly useful for cisplatin studies. These studies are planned.Additional future work includes the synthesis of semi-flexible (glycol) and flexible (alkyl) linkers to evaluate structure-activity relationships.iii ACKNOWLEDGEMENTS

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Convenient Iterative Synthesis of an Octameric Tetracarboxylate-Functionalized Oligophenylene Rod with Divergent End Groups

Cited by 47 publications

References 28 publications

Rhodamine analogs for molecular ruler applications

Rhodamine analogs for molecular ruler applications

Precise Synthesis of Molecularly Defined Oligomers and Polymers by Orthogonal Iterative Divergent/Convergent Approaches

Custom Fluorophores for Investigating the Cellular Uptake Mechanisms and Side-Effects of Pharmaceuticals

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