Aminomethyl Polystyrene Research Articles

Development of Self-Indicating Resin

Previously, we have reported the development and application of self-indicating resins (SIR), materials which can indicate presence or absence of amines in the reaction solution by the conspicuous color change of a phenolsulfophthalein type dye immobilized on resin beads [2a]. Although the functionality necessary for attaching the dye to the resins could be readily introduced by the Suzuki-Miyaura coupling during the synthesis of the SIR 1, this approach was only applicable to the dyes containing suitable functionality for the cross-coupling reaction. In this article we describe a new approach of immobilizing the indicating dyes onto the resin support. The dyes suitable for loading onto aminomethyl polystyrene (PS) resin were prepared by Friedel-Crafts reaction of 2-sulfoterephthalic anhydride with a wide range of phenols. Using this new route, the SIR 6c was readily prepared in >100g quantities. Use of the SIR 6c in the synthesis of a 144 member urea library was demonstrated and the SIR successfully indicated the endpoint of the reaction between amines and isocyanates.

PREPARATION OF POLYSTYRENE BEADS CONTAINING SULFONAMIDE GROUPS AND THEIR APPLICATION TO POLYMERIC BIOCIDES

A novel series of polystyrene (PS) beads containing various sulfonamide groups was prepared, and their chemical stabilities in an aqueous solution were tested in order to determine their ability to inactivate microbes. By reacting aminomethyl polystyrene (AM PS) beads or carboxy polystyrene beads with various benzenesulfonic acid derivatives, the sulfonamide groups were introduced on the PS beads. The characteristics of the product beads were analyzed by elementary analysis after the substitution of various sulfonamide groups. Energy Dispersive Spectroscopy (EDS), and FT-IR analysis were used to analyze the elemental functional group composition, respectively. The hydrolytic stabilities of the PS beads containing various sulfonamide groups along with the relationship between the swelling ratio and their hydrophilicity were investigated. The antibacterial activity of the beads was determined by their ability to inactivate E. coli. This study reports that PS beads containing sulfonamide groups had lasting antibacterial efficacy over a satisfactory period, whilst maintaining their chemical stabilities against hydrolysis. The 8 synthesized polymer beads exhibited antibacterial ability.

Synthesis of polymer-bound 4-acetoxy-3-phenylbenzaldehyde derivatives: applications in solid-phase organic synthesis.

Aminomethyl polystyrene resin was reacted with 4-(5'-formyl-2'-hydroxyphenyl)benzoic acid and 4-(5'-formyl-2'-hydroxyphenyl)phenyl propionic acid, respectively, in the presence of 1-hydroxybenzotriazole and 1,3-diisopropylcarbodiimide to yield polymer-bound benzaldehydes. The phenolic group in resins was acetylated with acetic anhydride to afford two polymer-bound 4-acetoxybenzaldehydes. The reductive amination of polymer-bound linkers by amines and sodium triacetoxyborohydride, followed by sulfonylation with arylsulfonyl chloride derivatives in the presence of pyridine and the cleavage with TFA/DCM/H2O, produced pure sulfonamides.

Recyclable Polymer-Supported Organolanthanide Hydroamination Catalysts. Immobilization and Activation via Dynamic Transamination

A series of divinylbenzene cross-linked, amino-functionalized polystyrene resins such as aminomethylated polystyrenes of varying mesh size, piperazinomethyl polystyrene, 1,12-diaminododecanetrityl resin, 1,7-diaminoheptanetrityl resin, 1,2-diaminoethanetrityl resin, 1,4-bis-(aminomethyl)benzenetrityl resin, N-(2-aminoethyl)aminomethyl polystyrene, cis-1,2-diaminocyclohexanetrityl resin, and trans-1,2-diaminocyclohexanetrityl resin are used as supports for the intramolecular hydroamination/cyclization precatalysts Cp‘2SmCH(SiMe3)2, Cp‘2LaCH(SiMe3)2 (Cp‘ = η5-Me5C5), and CGCSmN(SiMe3)2 (CGC = Me2Si[(η5-Me4C5)(tBuN)]). It is shown that these catalyst precursors can be immobilized on the polymer supports via transaminative protonolysis to give the corresponding bound precatalysts, which, in the presence of aminoalkene substrates, are transaminatively released for efficient homogeneous intramolecular hydroamination/cyclization processes. Upon substrate consumption, the catalysts are readsorbed on the supports. In many cases, these catalysts exhibit activities comparable to the homogeneous precursors and are recoverable/recyclable with only minor to moderate loss of activity, depending on the particular resin amino substituents.

Application of a Solid-Phase β-Triphosphitylating Reagent in the Synthesis of Nucleoside β-Triphosphates

A beta-triphosphitylating reagent was subjected to reaction with aminomethyl polystyrene resin-bound p-acetoxybenzyl alcohol to yield the corresponding polymer-bound beta-triphosphitylating reagent. The solid-phase reagent was reacted with unprotected nucleosides (e.g., 3'-azido-3'-deoxythymidine, cytidine, thymidine, uridine, inosine, or adenosine) in the presence of 1H-tetrazole. Polymer-bound nucleosides underwent oxidation with t-butyl hydroperoxide, deprotection of cyanoethoxy groups with DBU, and the acidic cleavage, respectively, to afford only monosubstituted 5'-O-beta-triphosphorylated nucleosides.

Heterogeneous Baeyer–Villiger oxidation of ketones using hydrogen peroxide as oxidant catalyzed by aminomethyl polystyrene resin-supported tin complex

An aminomethyl polystyrene resin supported tin complex (PS–Sn) catalyst was prepared by a simple procedure and found to be an active and selective catalyst for the Baeyer–Villiger (B–V) oxidation of cyclic and acyclic ketones including 2-adamantanone, 2-methylcyclohexanone, cyclohexanone, 2- tert-butylcyclohexanone, 4- tert-butylcyclohexanone, 4-methylcyclohexanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, and cyclopentanone using 30% hydrogen peroxide as oxidant.

A convenient semicarbazide resin for the solid-phase synthesis of peptide ketones and aldehydes

Use of a semicarbazide resin for the solid-phase preparation of peptide ketones and aldehyde led to optimal results in terms of both purity of the final product and overall yield. This resin was prepared without complication by activation of the commercial available aminomethyl polystyrene with CDI at room temperature, followed by treatment with tert-butyl carbazate. Furthermore, the TNBSA colorimetric assay has been adapted for checking the incorporation of the carbonyl moiety onto hydrazine-based resins.

Microwave‐Assisted Functionalization of Solid Supports for Rapid Loading of Nucleosides

Ultra-fast and efficient functionalization of solid supports such as controlled-pore glass (CPG), amino methyl polystyrene, and Tentagel has been achieved using microwave-assisted procedures. Both amino- and carboxy-terminated supports are easily prepared within minutes, in a reproducible manner, using microwave-assisted methodologies. The resulting functionalized supports are efficiently coupled to nucleosides using dimethylformamide as a solvent in conjunction with a specially designed reactor and workstation called LOTUS. Using these improved protocols, CPG with loadings of 75 to 85 micromol/g can be prepared on a large scale within 3 to 4 days starting from native CPG, as opposed to traditional methods that require 10 to 15 days to achieve the same objective. In addition, the methods described here can potentially be employed for rapid functionalization of other solid matrices such as beads, slides, and pins for applications in microarrays or combinatorial chemistry.

Selective Diphosphorylation, Dithiodiphosphorylation, Triphosphorylation, and Trithiotriphosphorylation of Unprotected Carbohydrates and Nucleosides

[chemical reaction: see text]. Aminomethyl polystyrene resin-bound linkers of p-acetoxybenzyl alcohol were subjected to reactions with diphosphitylating and triphosphitylating reagents to yield the corresponding polymer-bound diphosphitylating and triphosphitylating reagents, respectively. A number of unprotected carbohydrates and nucleosides were reacted with the polymer-bound reagents. Oxidation with tert-butyl hydroperoxide or sulfurization with Beaucage's reagent, followed by removal of cyanoethoxy group with DBU and the acidic cleavage, respectively, afforded only one type of monosubstituted nucleoside and carbohydrate diphosphates, dithiodiphosphates, triphosphates, and trithiotriphosphates with high regioselectivity.

New Titanium Imido Synthons: Syntheses and Supramolecular Structures

Reactions of Ti(NMe(2))(2)Cl(2) with a wide range of primary alkyl and arylamines RNH(2) afforded the corresponding 5-coordinate imido titanium compounds Ti(NR)Cl(2)(NHMe(2))(2) (R = (t)Bu (1), (i)Pr (2), CH(2)Ph (3), Ph (4), 2,6-C(6)H(3)Me(2) (5), 2,6-C(6)H(3)(i)Pr(2) (6), 2,4,6-C(6)H(2)F(3) (7), 2,3,5,6-C(6)HF(4) (8), C(6)F(5) (9), 4-C(6)H(4)Cl (10), 2,3,5,6-C(6)HCl(4) (11), 2-C(6)H(4)CF(3) (12), 2-C(6)H(4)(t)Bu (13)). The compounds 1-13 are monomeric in solution but in the solid state form either N-H...Cl hydrogen bonded dimers or chains or perfluorophenyl pi-stacked chains, depending on the imido R-group. The compound 13 was also prepared in a "one-pot" synthesis from RNH(2) and Ti(NMe(2))(4) and Me(3)SiCl. Reaction of certain Ti(NR)Cl(2)(NHMe(2))(2) compounds with an excess of pyridine afforded the corresponding bis- or tris-pyridine analogues [Ti(NR)Cl(2)(py)(x)](y) (x = 3, y = 1; x = y = 2), and the structure of Ti(2)(NC(6)F(5))(2)Cl(2)(mu-Cl)(2)(py)(4) shows pi-stacking of perfluorophenyl rings. Reaction of Ti(NMe(2))(2)Cl(2) with cross-linked aminomethyl polystyrene gave quantitative conversion to the corresponding solid-supported titanium imido complex. This paper represents the first detailed study of how supramolecular structures of imido compounds may be influenced by simple variation of the imido ligand N-substituent.

Combinatorial Solid-Phase Synthesis of 6-Hydroxy-1,2,3,4-tetrahydro-β-carbolines from l-5-Hydroxytryptophan

A library of biologically relevant 6-hydroxy-tetrahydro-beta-carbolines (6-OH-THBCs) based on the L-5-OH-tryptophan scaffold was prepared. A solid-phase synthesis was developed, utilizing aminomethyl polystyrene resin and solid-phase-optimized reactions, such as Pictet-Spengler condensation. The library was designed such that three points of diversity would be readily introduced, making the strategy potentially suitable for generation of a large number of compounds.

Preparation of Core−Shell-Type Aminomethyl Polystyrene Resin and Characterization of Its Functional Group Distribution

ADVERTISEMENT RETURN TO ISSUEPREVReportNEXTPreparation of Core−Shell-Type Aminomethyl Polystyrene Resin and Characterization of Its Functional Group DistributionTae-Kyung Lee, Sun-Jong Ryoo, Jang-Woong Byun, Sang-Myung Lee, and Yoon-Sik LeeView Author Information School of Chemical and Biological Engineering, Seoul National University, Seoul 151-742, Korea, and BeadTech Inc., Seoul National University Research Park, Suite 313, Seoul 151-818, Korea Cite this: J. Comb. Chem. 2005, 7, 2, 170–173Publication Date (Web):January 12, 2005Publication History Received13 August 2004Published online12 January 2005Published inissue 1 March 2005https://doi.org/10.1021/cc0498635Copyright © 2005 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views684Altmetric-Citations15LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (148 KB) SUBJECTS:Aromatic compounds,Fluorescence,Functional groups,Layers,Organic polymers Get e-Alerts

Solid-Phase Reagents for Selective Monophosphorylation of Carbohydrates and Nucleosides

Two classes of aminomethyl polystyrene resin-bound linkers of p-acetoxybenzyl alcohol were subjected to reactions with 2-cyanoethyl N,N-diisopropylchlorophosphoramidite to produce the corresponding polymer-bound phosphitylating reagents. These were reacted with a number of unprotected nucleosides and carbohydrates in the presence of 1H-tetrazole. Oxidation with tert-butyl hydroperoxide followed by removal of the cyanoethoxy group with 1,8-diazabicyclo[5.4.0]undec-7-ene afforded the corresponding polymer-bound phosphate diesters. Acidic cleavage of the p-acetoxybenzyl alcohol linker yielded monophosphorylated products with high regioselectivity and trapped linkers on the resins that can be reused.

4-(9-fluorenylmethyloxycarbonyl)phenylhydrazine (FmPH): a new chromophoric reagent for quantitative monitoring of solid-phase aldehydes(1-3).

A direct method for quantifying solid-phase aldehydes has been developed, using a new reagent, 4-(9-fluorenylmethyloxycarbonyl)phenylhydrazine (FmPH). The FmPH reagent was synthesized in three steps (24% overall yield) from commercially available p-hydrazinobenzoic acid. Resin-bound aldehydes reacted quantitatively with FmPH, in the presence of trimethylorthoformate (TMOF) as a dehydrating agent, to form a highly conjugated, immobilized FmPH-hydrazone. Next, mild treatment of the hydrazone with an excess of piperidine-N,N-dimethylformamide (1:1) released the piperidine-dibenzofulvene adduct chromophore (epsilon(301nm) = 7800 M(-1) cm(-1)) from the support. FmPH quantitation of aldehydes proved to be a straightforward, sensitive, and reproducible technique for monitoring resin-bound aldehydes [albeit insufficiently reactive to allow reliable quantification of ketones]. The FmPH aldehyde assay is applicable to a range of solid supports, as demonstrated specifically for poly(ethylene glycol)-polystyrene (PEG-PS), aminomethylpolystyrene (AMP), and cross-linked ethoxylate acrylate resin (CLEAR).

Two dialkoxynaphthalene aldehydes as backbone amide linkers for solid-phase synthesis.

Two new solid-phase handles for backbone amide anchoring based on regioisomeric dialkoxynaphthalene aldehydes (NALdehydes) were synthesized in five convenient steps from the corresponding commercially available dihydroxynaphthalenes. The two NALdehydes were coupled to an aminomethyl polystyrene support, the first monomer attached by efficient reductive amination, and the secondary amine acylated to form naphthalene amide linker (NAL-1 and NAL-2) anchoring. After on-resin synthesis, release of peptides was effected with TFA/H(2)O (95:5), TFA/DCM (50:50), or low TFA concentrations. The properties of the NAL handles were evaluated in the solid-phase synthesis of a series of peptides, in which NAL-2 showed the best cleavage properties.

A novel class of chemically modified iodo-containing resins: design, synthesis and application to mass spectrometry-based proteome analysis.

A novel class of chemically modified iodo-containing resins with isotope-labeled tagging for mass spectrometry-based proteome analysis is described. This iodo-containing resin contains a thiol-reactive group that is used to capture the cysteine (Cys)-containing peptides from peptide mixtures, one 'tag' amino acid, and an aminomethyl polystyrene resin with Rink Amide Linker. The 'tag' amino acid is synthesized in both heavy and light isotope-coded forms and therefore permits the direct relative quantification of peptides/proteins through mass spectrometric analysis. In the iodo-containing resin strategy, the Cys-containing peptides of two samples covalently captured by either light or heavy iodo-containing resin were mixed and washed extensively under stringent conditions. Then the Cys-containing peptides were retrieved by acid-catalyzed elution. Finally, the eluted peptides were directly analyzed by micro liquid chromatography/mass spectrometry for identification and relative quantification. The iodo-containing resins were synthesized by a simple but effective method. Their abilities to identify and quantify the Cys-containing part in two samples were proved by the analysis of mixtures of amino acids, peptides and proteins.

Colorimetric monitoring of solid-phase aldehydes using 2,4-dinitrophenylhydrazine.

A simple and rapid method to achieve colorimetric monitoring of resin-bound aldehydes, based on ambient temperature reaction with 2,4-dinitrophenylhydrazine (DNPH) in the presence of dilute acid, has been developed as an adjunct to solid-phase organic synthesis and combinatorial chemistry. By this test, the presence of aldehydes is indicated by a red to dark-orange appearance, within a minute. Alternatively, resins that are free of aldehydes or in which aldehyde functions have reacted completely retain their original color. The DNPH test was demonstrated for poly(ethylene glycol)-polystyrene (PEG-PS), aminomethyl polystyrene (AMP), cross-linked ethoxylate acrylate resin (CLEAR), and acryloylated O,O'-bis(2-aminopropyl)poly(ethylene glycol) (PEGA) supports and gave results visible to the naked eye at levels as low as 18 micromol of aldehyde per gram of resin.

Hydrogenation of five‐membered heterocycles of polymer‐supported palladium catalyst at normal temperature and pressure

AbstractTo modify the surface of aminomethyl polystyrene, grafting of hyperbranched dendritic polyamidoamine, a new class of topological macromolecules, onto the surface was investigated. It was found that hyperbranched dendritic polyamidoamine was propagated from aminomethyl polystyrene surface by repeating two processes: (1) Michael addition; (2) amidation. Furthermore, salicylal (SA) readily postgrafted to the hyperbranched dendritic polyamidoamine‐grafted‐aminomethyl polystyrene. Finally, catalytic hydrogenations of pyrrole, furan and thiophene were investigated by the modifying polyamidoamine‐grafted aminomethyl polystyrene with SA (MPGAPS)‐supported palladium catalyst. The double‐bond of the ring was hydrogenated to single‐bond ring of tetrahydro‐compound at first, then the ring is broken directly. In general, these reactions were degradation under reduction. UV absorbance spectroscopy, gas chromatography (GC), and power of hydrogen (PH) detection were used to analyze the reactants and products, and infrared (IR), X‐ray photoelectron spectroscopy (XPS) and inductively coupled plasma‐atomic emission spectrometry (ICP‐AES) characterized the catalyst. Copyright © 2004 John Wiley & Sons, Ltd.

Improving resins for solid phase synthesis: incorporation of 1-[2-(2-methoxyethoxy)ethoxy]-4-vinyl-benzene

The preparation, characterisation and application of a series of non-grafted polystyrene (PS) resins containing a styrenic methoxypoly(ethylene glycol) (MPEG) derivative is presented. These novel PS-MPEG resins were designed to balance swelling and solvation with improved handling. The monomer, 1-[2-(2-methoxyethoxy)ethoxy]-4-vinyl-benzene, contained an inert phenyl ether linkage designed to provide broad chemical compatibility and stability, yet imparting all the favourable properties of the PEG group into the new resin, whilst maintaining a high loading capacity. The synthetic performance of the new resins compared very favourably to those of TentaGel™, ArgoGel™ and aminomethyl PS.

High-yield immobilization of a puromycin analogue for the solid support synthesis of aminoacyl-tRNA fragments.

[reaction: see text] An efficient procedure for the immobilization of 3'-deoxy-3'-(O-methyltyrosyl)aminoadenosine was developed. A poly(ethylene glycol)-derived diacid linker/spacer was attached to aminomethyl polystyrene. Coupling of the 2'-hydroxy instead of the 2'-O-succinylated ribonucleoside resulted in high immobilization yields (over 80%) and allowed for the recovery of valuable unreacted material. This specific procedure should be applicable to other ribonucleosides containing a bulky modification at the 3'-position and can be used for the stepwise construction of 3'-aminoacyl- or 3'-peptidyl-RNA conjugates.