Redox-switched crown ethers monocrown-biscrown interconversion coupled with redox of a thiol-disulfide couple

Minami, Takahide; Shinkai, Seiji; Manabe, Osamu

doi:10.1016/s0040-4039(00)85787-1

Cited by 19 publications

(7 citation statements)

References 12 publications

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“…Reagents and conditions: (i) see ref. [67] ; (ii) Cl 2 CS, BaCO 3 , CH 2 Cl 2 , room temp. ; (iii) (ClCH 2 CO) 2 O, AcOEt, room temp.…”

Section: Resultsmentioning

confidence: 99%

“…Bis(crown ether)s containing disulfide bridges have attracted attention as redox-switchable systems, for their utility in ion extraction and ion transport across liquid membranes. [67,68] Cyclic disulfides are typically prepared by oxidative dimerisation of α,ωdithiols, [69Ϫ75] or α,ω-bisthiocyanates. [76Ϫ79] For this reason, we first carried out the synthesis of the bisthiocyanate derivative 11 (85%), by treatment of 4 with KSCN in refluxing acetone (see Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

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An Efficient Synthesis of Bis(calix[4]arenes), Bis(crown ether)-Substituted Calix[4]arenes, Aza-Crown Calix[4]arenes, and Thiaza-Crown Calix[4]arenes

2000

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The easy transformation of 5,11,17,23-tetra-tert-butyl-25,27bis(aminoethoxy)-26,28-dihydroxycalix[4]arene(2) into 5, 11,17,23-tetra-tert-butyl-26,28-dihydroxy-25,27-bis(2-isothiocyanoethoxy)calix[4]arene (3) and 5,11,17,23-tetra-tertbutyl-25,27-bis(chloroacetamidoethoxy)-26,28-dihydroxycalix[4]arene (4) has been exploited for the development of an efficient and expeditious synthesis of a variety of calix[4]3587 calix[4]arenes]. The functionality of compounds 2 and 3 allowed the formation of intramolecular bridges, leading to capped calix[4]arenes (compounds 5, 10, and 14) as well as to the construction of double calix[4]arene units by means of spacers containing thiourea or amide-sulfur groups (compounds 6 and 15, respectively). In addition, the bis(isothiocyanate) derivative 3 gave access to a high-yield preparation of heteroditopic bis(crown ether) calix[4]arenes (7−9) from commercial amino crown ethers.

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“…Reagents and conditions: (i) see ref. [67] ; (ii) Cl 2 CS, BaCO 3 , CH 2 Cl 2 , room temp. ; (iii) (ClCH 2 CO) 2 O, AcOEt, room temp.…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

An Efficient Synthesis of Bis(calix[4]arenes), Bis(crown ether)-Substituted Calix[4]arenes, Aza-Crown Calix[4]arenes, and Thiaza-Crown Calix[4]arenes

2000

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“…Downloaded from www.nrcresearchpress.com by 54.213.204 sodium channels that initiates a seizure corresponds chemically to the creation of a sodium-selective cyclodepsipeptide ionophore (26), by an oxidative process, as depicted schematically in Fig. The concept of "redox-switched" ionophores is not new. Shinkai and co-workers (28) and Raban et al (29) have reported the syntheses of a,w-dimercapto polyoxy compounds, which behave as pro-ionophores. In their reduced forms these compounds are poor ionophores; oxidation generates effective crown ether ionophores, whose cation selectivity depends on ring size.…”

Section: Hypothesismentioning

confidence: 99%

“…In their reduced forms these compounds are poor ionophores; oxidation generates effective crown ether ionophores, whose cation selectivity depends on ring size. The oxidation reaction exhibits a marked template effect (28), and it has been argued (29) that "chemically switchable pro-ionophore-ionophore couples can serve as models for biological "ion gates", structures in which ion transport is initiated by an external stim~lus. "~…”

Section: Hypothesismentioning

confidence: 99%

Phenceptin: a biomimetic model of the phenytoin receptor

Wolfe¹,

Bowers²,

Shin³

et al. 1988

Can. J. Chem.

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Can. J. Chem. 66, 2751(1988. 5,s-Diphenylhydanytoin (phenytoin) is the most widely used anticonvulsant drug, but has many side effects. Although its chemical mode of action is unknown, phenytoin is believed to function primarily by interference with the transport of sodium ions across the neuronal membrane. Structure-activity and lipophilicity-activity studies suggest that the drug interacts with its receptor through hydrogen bonding to the N3-C4 amide bond, and an aromatic-aromatic interaction with the C5 substituent. Since sodium channels are cysteine-rich peptides, whose function depends upon the cysteineecystine redox process, it has been hypothesized that the action of the phenytoin receptor may be mimicked by a properly designed cyclodepsipeptide containing a cystinyl moiety, a cavity lined with five oxygen atoms oriented in the trigonal-bipyramidal manner appropriate for selective transport of sodium ions, and a site for the binding of phenytoin. A computer programme and strategy were developed to permit the three-dimensional structures of potential target molecules to be viewed, prior to synthesis. Use of this programme led to the discovery of Boc-~-cystinyl-glycyI-~-prolyl-glycyl-~-prolyl-~-cystine-OCHPh. This compound, termed phenceptin, was synthesized from a linear precursor containing tert-butoxycarbonyl protection at the N-terminus, benzhydryl ester protection at the C-terminus, and trityl protection at sulfur. Detritylation and cyclization to phenceptin were accomplished with iodine in methanol-pyridine. Using an n-octanol membrane to study the kinetics of ion transport, phenceptin was found to transport sodium ions selectively, but only in its oxidized, cyclic form. This transport was inhibited significantly by one mol-equiv. of phenytoin, and not at all by biologically inactive analogs of the drug. The nature of the binding of phenytoin to phenceptin was examined by nuclear magnetic resonance, in n-CsD17-OH solvent, and found to involve hydrogen bonding of the drug to a glycine residue whose oxygen atom is involved in complexation to sodium ions. SAUL WOLFE, RAYMOND JOHN BOWERS, HEE-SOOK SHIN, CHANG-KOOK SOHN, DONALD FREDRIC WEAVER ET KIYULLYANG. Can. J. Chem. 66, 2751 (1988). La diphCnyl-5,s hydantoyne (phtnytoi'ne) est le mtdicament le plus utilist comme anticonvulsivant; toutefois, il provoque de nombreuses rkactions secondaires. MCme si son mode d'action chimique est inconnu, on croit que la phtnytoi'ne agit principalement par interftrence avec le transport des ions sodium a travers les membranes neuronales. Des etudes de structure/activitC et caractere liphophilique/activitt suggkrent que la drogue interagit avec son rtcepteur par le biais de liaisons hydrogknes avec la liaison amide N3-C4 et par une interaction aromatique/aromatique avec le substituant en C5. Puisque les canaux du sodium sont des peptides riches en cysttine dont la fonction dtpend du processus redox cysteine/cystine, il a Ct C suggCrC que l'on pourrait rCpliquer l'action du rCcepteur de la phCnytoi'ne a l'aide d'un cyclod...

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“…The various macrocyclic compounds such as crown ether and calixarene [1][2][3] containing redox-active centers have been utilized for the development of advancing chemical sensor technology. Several excellent quinone and anthraquinone based redox-switchable ligands for cations were developed by Gokel and Echegoyen.…”

Section: Introductionmentioning

confidence: 99%

HSO₄^-Anion Selective Urea Calix[4]diquinone Receptor

2002

Bulletin of the Korean Chemical Society

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Redox-switched crown ethers monocrown-biscrown interconversion coupled with redox of a thiol-disulfide couple

Cited by 19 publications

References 12 publications

An Efficient Synthesis of Bis(calix[4]arenes), Bis(crown ether)-Substituted Calix[4]arenes, Aza-Crown Calix[4]arenes, and Thiaza-Crown Calix[4]arenes

An Efficient Synthesis of Bis(calix[4]arenes), Bis(crown ether)-Substituted Calix[4]arenes, Aza-Crown Calix[4]arenes, and Thiaza-Crown Calix[4]arenes

Phenceptin: a biomimetic model of the phenytoin receptor

HSO₄^-Anion Selective Urea Calix[4]diquinone Receptor

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Redox-switched crown ethers monocrown-biscrown interconversion coupled with redox of a thiol-disulfide couple

Cited by 19 publications

References 12 publications

An Efficient Synthesis of Bis(calix[4]arenes), Bis(crown ether)-Substituted Calix[4]arenes, Aza-Crown Calix[4]arenes, and Thiaza-Crown Calix[4]arenes

An Efficient Synthesis of Bis(calix[4]arenes), Bis(crown ether)-Substituted Calix[4]arenes, Aza-Crown Calix[4]arenes, and Thiaza-Crown Calix[4]arenes

Phenceptin: a biomimetic model of the phenytoin receptor

HSO4-Anion Selective Urea Calix[4]diquinone Receptor

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HSO₄^-Anion Selective Urea Calix[4]diquinone Receptor