链接化学与聚合 相关内容.docx

1、链接化学与聚合 相关内容Prof. K. B. Sharpless, Prof. M. G. FinnDepartment of ChemistryThe Scripps Research Institute10550 North Torrey Pines RoadLa Jolla, CA 92037 (USA)Fax: (+1) 858-784-7562E-mail: sharplesscripps.eduDr. H. C. KolbVice President of ChemistryCoelacanth CorporationEast Windsor, NJ 08520 (USA)Jou

2、rnal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 56995707 (2006)ABC-Type Hetero-Arm Star Terpolymers Through “Click” Chemistry链接所需含炔化合物，同时含有ATRP引发剂、TEMPO引发剂60oC ATRP MMA聚合、125oC TEMPO St聚合80oC ATRP tBA聚合、末端转化成叠氮功能基单羟基聚乙二醇PEG、对甲苯磺酰氯，将末端转化成对甲苯磺酰基，再转化成叠氮功能基三臂不同聚合物主链的星型聚合物Journal of Polymer

3、Science: Part A: Polymer Chemistry, Vol. 44, 64586465 (2006)A3-Type Star Polymers via Click ChemistryAnalytical Chemistry, Vol. 78, No. 14, July 15, 2006 4969-4975“Click Chemistry” in the Preparation of Porous Polymer-Based Particulate Stationary Phases for -HPLC Separation of Peptides and ProteinsT

4、he copper(I)-catalyzed (3 + 2) azide-alkyne cycloaddition, an element of the “click chemistry” popularized by Sharpless group,7 is a very efficient coupling reaction that provides an ideal reactivity profile for this purpose. Equation 1 shows a general scheme of the Cu(I)-catalyzed reaction of a ter

5、minal alkyne with a terminal azide affording a 1,4-disubstituted triazole ring:Cu(I)催化的3+2叠氮-炔烃环加成是Sharpless研究小组广泛应用的链接化学的重要反应，是非常有效的偶联反应，能够保证理想的反应活性满足研究目的。该反应在有机化学中是1,4-二取代三唑环的合成方法，原料是末端炔烃和末端叠氮化合物。This reaction has already been widely used for the synthesis of substituted triazoles in solution. 8-1

6、2 Because azide and alkyne functionalities do not interfere with common biological processes, the copper-catalyzed azide-alkyne cycloaddition has been used for profiling enzyme activity13-17 and to incorporate new functionalities in proteins,18 cells,19 and viruses.20 This “click” reaction was also

7、applied for the preparation and functionalization of dendrimers21,22 as well as for the synthesis23 and modification24 of linear polymers. In addition, the utility of this reaction has also been demonstrated in chemical modifications performed on solid polymer supports. For example, it has been inte

8、grated with solidphase peptide synthesis to produce peptidotriazoles25,26 and for the installation, via a “click linker”, of sensitive functionalities on Merrifield resin for solid-phase organic synthesis.27,28 Finally, Puna et al. have recently prepared an azide derivative of diaminodipropylamine a

9、garose beads and used this click reaction to immobilize alkyne-containing versions of biotin and a hexapeptide.29 They also used a complementary alkyne derivative of agarose to attach 4-azido-N-(4-(4-oxobutoxy)phenyl)butyramide; this aldehydecontaining ligand was then used for the selective separati

10、on of a specific antibody.Chem. Commun., 2005, 43334335Click-chemistry as an efficient synthetic tool for the preparation of novel conjugated polymersChem. Commun., 2005, 45814583Efficient microwave-assisted synthesis of multivalent dendrimeric peptides using cycloaddition reaction (click) chemistry

11、Chem. Commun., 2006, 40104012Synthesis of star-shaped poly(-caprolactone) via click chemistry and supramolecular click chemistryChem. Commun., 2006, 39333935Functionalization of polymers with phosphorescent iridium complexes via click chemistryChem. Commun., 2006, 50515053RAFT and click chemistry: A

12、 versatile approach to well-defined block copolymers近乎对称的三唑环链接的RAFT聚合所得聚苯乙烯Bioconjugate Chem. 2007, 18, 263-267Soluble Camptothecin Derivatives Prepared by Click Cycloaddition Chemistry on Functional Aliphatic Polyesters喜树碱（可用于癌症的治疗）Sn(II)-mediated ring-opening copolymerization of -propargyl-valerol

13、actone and -caprolactone was conducted to give aliphatic polyester 1 with a nearly 1:1 ratio of the two monomers, as confirmed by integration of the 1H NMR spectrum of the polymer. Gel permeation chromatography of polyester 1, performed in THF against polystyrene molecular weight standards, gave an

14、estimated number-average molecular weight (Mn) of 9200 g/mol and a polydispersity index (PDI, Mw/Mn) of 1.17.Synthesis of 6-Azidohexanoic Acid (2). 6-Bromohexanoic acid (5.0 g, 25.6 mmol) and sodium azide (8.37 g, 128 mmol) were dissolved in DMSO and stirred at room temperature for 8 h. The reaction

15、 mixture was then dissolved in CH2Cl2, washed with water, brine, and NaHCO4(aq), dried over MgSO4, and concentrated by rotary evaporation. Residual DMSO was removed by Kugelrohr distillation at 120 C. Distillation at 160 C gave 6-azidohexanoic acid 2 as a colorless liquid (2.98 g, 74%). MS-ESI (m/z)

16、: M + Na+ calculated for C6H11N3O2 180.1, found 180.1. 1H NMR (CDCl3, 300 MHz): (CHCl3 ) 7.26 ppm) 11.43 (br, 1H, COOH), 3.28 (t, 2H, CH2N3), 2.38 (t, 2H, CH2COOH), 1.65 (m, 4H, CH2CH2CH2CH2CH2), 1.43 (m, 2H, CH2CH2CH2CH2CH2) ppm. 13C NMR (CDCl3, 75 MHz): (CHCl3 ) 77.0 ppm) 180.1 (CdO), 51.2 (CH2N3)

17、, 33.9 (CH2COOH), 28.5 (CH2CH2N3), 26.2 (CH2CH2CH2N3), 24.2 (CH2CH2COOH) ppm. IR(ATR): NdNdN 2090 cm-1.Bioconjugate Chem. 2007, 18, 579-584Synthesis of Symmetrical and Unsymmetrical PAMAM Dendrimers by Fusion between Azide- and Alkyne-Functionalized PAMAM DendronsBiomacromolecules 2006, 7, 3104-3111

18、“Clickable” PEG-Dendritic Block CopolymersBiomacromolecules 2007, 8, 744-749Surface-Initiated, Atom Transfer Radical Polymerization of Oligo(ethylene glycol) Methyl Ether Methacrylate and Subsequent Click Chemistry for BioconjugationDesigned Monomers and Polymers, Vol. 8, No. 6, pp. 533546 (2005)Cha

19、racterization of ,-dihydroxypolystyrene by gradient polymer elution chromatography and two-dimensional liquid chromatographyAngew. Chem. Int. Ed. 2006, 45, 5292 5296“Click” Chemistry by Microcontact Printing Angew. Chem. Int. Ed. 2001, 40, 2004 - 2021Click Chemistry: Diverse Chemical Function from a

20、 Few Good ReactionsJournal of Polymer Science: Part A: Polymer Chemistry, Vol. 42, 43924403 (2004)Click Chemistry in Materials Synthesis. 1. Adhesive Polymers from Copper-Catalyzed Azide-Alkyne CycloadditionJournal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 55135518 (2006)Click Chemistr

21、y in Materials Synthesis. II. Acid-Swellable Crosslinked Polymers Made by Copper-Catalyzed AzideAlkyne CycloadditionMolecular Imaging Vol 5, No. 2, April-June 2006, pp. 22-128“Clickable” Nanoparticules for Targeted ImagingMacromol. Rapid Commun. 2005, 26, 514518Combining Atom Transfer Radical Polyme

22、rization and Click Chemistry: A Versatile Method for the Preparation of End-Functional PolymersJournal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 52035217 (2006)Facile Syntheses of Surface-Functionalized Micelles and Shell Cross-Linked NanoparticlesChem. Eur. J. 2006, 12, 6776 6786Fluor

23、ogenic 1,3-Dipolar Cycloaddition within the Hydrophobic Core of a Shell Cross-Linked NanoparticleJ. AM. CHEM. SOC. 2004, 126, 15020-15021Dendronized Linear Polymers via “Click Chemistry”J. AM. CHEM. SOC. 2006, 128, 4823-4830Synthesis of Neoglycopolymers by a Combination of “Click Chemistry” and Livi

24、ng Radical PolymerizationJ. AM. CHEM. SOC. 2006, 128, 9318-9319Assembly of Ultrathin Polymer Multilayer Films by Click ChemistryJ. AM. CHEM. SOC. 2006, 128, 11356-11357Toward the Syntheses of Universal Ligands for Metal Oxide Surfaces: Controlling Surface Functionality through Click ChemistryJ. AM.

25、CHEM. SOC. 2005, 127, 14942-14949Orthogonal Approaches to the Simultaneous and Cascade Functionalization of Macromolecules Using Click ChemistryJ. AM. CHEM. SOC. 2006, 128, 6564-6565Synthesis of Degradable Model Networks via ATRP and Click ChemistryJ. AM. CHEM. SOC. 2006, 128, 11360-11361Synthesis o

26、f 3-Miktoarm Stars and 1st Generation Mikto Dendritic Copolymers by “Living” Radical Polymerization and “Click” ChemistryJ. AM. CHEM. SOC. 2006, 128, 12084-12085A Versatile New Monomer Family: Functionalized 4-Vinyl-1,2,3-Triazoles via Click ChemistryMacromol. Rapid Commun. 2007, 28, 1554Click Chemi

27、stry in Polymer and Materials ScienceJournal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 56995707 (2006) 1Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 64586465 (2006) 2Analytical Chemistry, Vol. 78, No. 14, July 15, 2006 4969-4975 3Chem. Commun., 2005, 43334335 4Chem.

28、Commun., 2005, 45814583 4Chem. Commun., 2006, 40104012 5Chem. Commun., 2006, 39333935 6Chem. Commun., 2006, 50515053 7Bioconjugate Chem. 2007, 18, 263-267 8Bioconjugate Chem. 2007, 18, 579-584 9Biomacromolecules 2006, 7, 3104-3111 10Biomacromolecules 2007, 8, 744-749 10Designed Monomers and Polymers

29、, Vol. 8, No. 6, pp. 533546 (2005) 11Angew. Chem. Int. Ed. 2006, 45, 5292 5296 11Angew. Chem. Int. Ed. 2001, 40, 2004 - 2021 12Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 42, 43924403 (2004) 13Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 55135518 (2006) 14Molecular

30、 Imaging Vol 5, No. 2, April-June 2006, pp. 22-128 15Macromol. Rapid Commun. 2005, 26, 514518 15Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 52035217 (2006) 16Chem. Eur. J. 2006, 12, 6776 6786 17J. AM. CHEM. SOC. 2004, 126, 15020-15021 17J. AM. CHEM. SOC. 2006, 128, 4823-4830 18J. AM. CHEM. SOC. 2006, 128, 9318-9319 19J. AM. CHEM. SOC. 2006, 128, 11356-11357 19J. AM. CHEM. SOC. 2005, 127, 14942-14949 19J. AM. CHEM. SOC. 2006, 128, 6564-6565 20J. AM. CHEM. SOC. 2006, 128, 11360-11361 20J. AM. CHEM. SOC. 2006, 128, 12084-12085 21Macromol. Rapid Commun. 2007, 28, 1554 22