In this study, a novel pyrazole–carbodithioate-based chain transfer agent (CTA) featuring an aldehyde group (CTA-CHO) was designed and synthesized for RAFT polymerization. The obtained CTA-CHO was employed for the RAFT polymerization of styrene to afford well-defined polystyrenes bearing an aldehyde at their chain ends with low Ð values (~1.1). In addition, the reactivity of the aldehyde moiety at the end of the chain was precisely evaluated, while the Passerini three-component reaction was successfully performed on the aldehyde group.
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Zhu J, Bienaymé H. Multicomponent reactions. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA; 2005.
Armstrong RW, Combs AP, Tempest PA, Brown SD, Keating TA. Multiple-component condensation strategies for combinatorial library synthesis. Acc Chem Res. 1996;29:123–31. https://doi.org/10.1021/ar9502083
Dömling A. Recent developments in isocyanide based multicomponent reactions in applied chemistry. Chem Rev. 2006;106:17–89. https://doi.org/10.1021/cr0505728
Dömling A, Wang W, Wang K. Chemistry and biology of multicomponent reactions. Chem Rev. 2012;112:3083–135. https://doi.org/10.1021/cr100233r
Rotstein BH, Zaretsky S, Rai V, Yudin AK. Small heterocycles in multicomponent reactions. Chem Rev. 2014;114:8323–59. https://doi.org/10.1021/cr400615v
Touré BB, Hall DG. Natural product synthesis using multicomponent reaction strategies. Chem Rev. 2009;109:4439–86. https://doi.org/10.1021/cr800296p
Wessjohann LA, Rivera DG, Vercillo OE. Multiple multicomponent macrocyclizations (MiBs): a strategic development toward macrocycle diversity. Chem Rev. 2009;109:796–814. https://doi.org/10.1021/cr8003407
Kreye O, Türünç O, Sehlinger A, Rackwitz J, Meier MAR. Structurally diverse polyamides obtained from monomers derived via the Ugi multicomponent reaction. Chem Eur J. 2012;18:5767–76. https://doi.org/10.1002/chem.201103341
Kreye O, Tóth T, Meier MAR. Introducing multicomponent reactions to polymer science: passerini reactions of renewable monomers. J Am Chem Soc. 2011;133:1790–2. https://doi.org/10.1021/ja1113003
Zhu C, Yang B, Zhao Y, Fu C, Tao L, Wei Y. A new insight into the Biginelli reaction: the dawn of multicomponent click chemistry? Polym Chem. 2013;4:5395–5400. https://doi.org/10.1039/C3PY00553D
Zhang Q, Zhang Y, Zhao Y, Yang B, Fu C, Wei Y, et al. Multicomponent Polymerization System Combining Hantzsch Reaction and Reversible Addition–Fragmentation Chain Transfer to Efficiently Synthesize Well-Defined Poly(1,4-dihydropyridine)s. ACS Macro Lett. 2015;4:128–32. https://doi.org/10.1021/mz500734c
Kakuchi R, Theato P. Three-Component Reactions for Post-Polymerization Modifications. ACS Macro Lett. 2013;2:419–22. https://doi.org/10.1021/mz400144q
Lee I-H, Kim H, Choi T-L. Cu-Catalyzed Multicomponent Polymerization To Synthesize a Library of Poly(N-sulfonylamidines). J Am Chem Soc. 2013;135:3760–3. https://doi.org/10.1021/ja312592e
Deng XX, Cui Y, Du FS, Li ZC. Functional highly branched polymers from multicomponent polymerization (MCP) based on the ABC type Passerini reaction. Polym Chem. 2014;5:3316–20. https://doi.org/10.1039/c3py01705b
Jee J-A, Spagnuolo LA, Rudick JG. Convergent synthesis of dendrimers via the passerini three-component reaction. Org Lett. 2012;14:3292–5. https://doi.org/10.1021/ol301263v
Li L, Kan X-W, Deng X-X, Song C-C, Du F-S, Li Z-C. Simultaneous dual end-functionalization of peg via the passerini three-component reaction for the synthesis of ABC miktoarm terpolymers. J Polym Sci Part A. 2013;51:865–73. https://doi.org/10.1002/pola.26443
Deng X-X, Li L, Li Z-L, Lv A, Du F-S, Li Z-C. Sequence Regulated Poly(ester-amide)s Based on Passerini Reaction. ACS Macro Lett. 2012;1:1300–3. https://doi.org/10.1021/mz300456p
Yang B, Zhao Y, Fu CK, Zhu CY, Zhang YL, Wang SQ, et al. Introducing the Ugi reaction into polymer chemistry as a green click reaction to prepare middle-functional block copolymers. Polym Chem. 2014;5:2704–8. https://doi.org/10.1039/c4py00001c
Kakuchi R, Theato P. Efficient multicomponent postpolymerization modification based on kabachnik-fields reaction. ACS Macro Lett. 2014;3:329–32. https://doi.org/10.1021/mz500139c
Moldenhauer F, Kakuchi R, Theato P. Synthesis of Polymers via Kabachnik-Fields Polycondensation. ACS Macro Lett. 2016;5:20–23. https://doi.org/10.1021/acsmacrolett.5b00720
Kakuchi R, Yoshida S, Sasaki T, Kanoh S, Maeda K. Multi-component post-polymerization modification reactions of polymers featuring lignin-model compounds. Polym Chem. 2018;9:2109–15. https://doi.org/10.1039/C7PY01923H
Zhang Y, Zhao Y, Yang B, Zhu C, Wei Y, Tao L. ‘One pot’ synthesis of well-defined poly(aminophosphonate)s: time for the Kabachnik–Fields reaction on the stage of polymer chemistry. Polym Chem. 2014;5:1857–62. https://doi.org/10.1039/C3PY01486J
Zhang Y, Zhao Y, Xia S, Tao L, Wei Y. A Facile Preparation of Mussel-Inspired Poly(dopamine phosphonate-co-PEGMA)s via a One-Pot Multicomponent Polymerization System. Macro Rapid Commun. 2020;41:1900533 https://doi.org/10.1002/marc.201900533
Iha RK, Wooley KL, Nyström AM, Burke DJ, Kade MJ, Hawker CJ. Applications of orthogonal click chemistries in the synthesis of functional soft materials. Chem Rev. 2009;109:5620–86. https://doi.org/10.1021/cr900138t
Golas PL, Matyjaszewski K. Marrying click chemistry with polymerization: expanding the scope of polymeric materials. Chem Soc Rev. 2010;39:1338–54. https://doi.org/10.1039/b901978m
Pound G, McKenzie JM, Lange RF, Klumperman B. Polymer-protein conjugates from omega-aldehyde endfunctional poly(N-vinylpyrrolidone) synthesised via xanthate-mediated living radical polymerisation. Chem Commun. 2008;27:3193–5. https://doi.org/10.1039/b803952f
Moad G, Rizzardo E, Thang SH. Living Radical Polymerization by the RAFT Process – A Third Update. Aust J Chem. 2012, 65 (8). https://doi.org/10.1071/ch12295.
Moad G. A Critical Survey of Dithiocarbamate Reversible Addition‐Fragmentation Chain Transfer (RAFT) Agents in Radical Polymerization. J Polym Sci Part A. 2018;57:216–27. https://doi.org/10.1002/pola.29199
Keddie DJ, Moad G, Rizzardo E, Thang SH. RAFT Agent Design and Synthesis. Macromolecules. 2012;45:5321–42. https://doi.org/10.1021/ma300410v
Li J, Yang S, Wang L, Wang X, Liu L. Thermoresponsive dynamic covalent polymers with tunable properties. Macromolecules. 2013;46:6832–42. https://doi.org/10.1021/ma400948j
Reader PW, Pfukwa R, Jokonya S, Arnott GE, Klumperman B. Synthesis of α,ω-heterotelechelic PVP for bioconjugation, via a one-pot orthogonal end-group modification procedure. Polym Chem. 2016;7:6450–6. https://doi.org/10.1039/C6PY01296E
Deng J, Liu X, Ma L, Cheng C, Sun S, Zhao C. Switching biological functionalities of biointerfaces via dynamic covalent bonds. J Mater Chem B. 2016;4:694–703. https://doi.org/10.1039/C5TB02072G
Jackson AW, Fulton DA. Dynamic Covalent Diblock Copolymers Prepared from RAFT Generated Aldehyde and Alkoxyamine End-Functionalized Polymers. Macromolecules. 2010;43:1069–75. https://doi.org/10.1021/ma902291a
Gardiner J, Martinez-Botella I, Tsanaktsidis J, Moad G. Dithiocarbamate RAFT agents with broad applicability – the 3,5-dimethyl-1H-pyrazole-1-carbodithioates. Polym Chem. 2016;7:481–92. https://doi.org/10.1039/c5py01382h
Gardiner J, Martinez-Botella I, Kohl TM, Krstina J, Moad G, Tyrell JH, et al. 4-Halogeno-3,5-dimethyl-1H-pyrazole-1-carbodithioates: versatile reversible addition fragmentation chain transfer agents with broad applicability. Polym Int. 2017;66:1438–47. https://doi.org/10.1002/pi.5423
Banerjee S, Guerre M, Améduri B, Ladmiral V. Syntheses of 2-(trifluoromethyl)acrylate-containing block copolymers via RAFT polymerization using a universal chain transfer agent. Polym Chem. 2018;9:3511–21. https://doi.org/10.1039/C8PY00655E
Willcock H, O’Reilly RK. End group removal and modification of RAFT polymers. Polym Chem. 2010;1:149–57. https://doi.org/10.1039/B9PY00340A
Uchiyama M, Satoh K, Kamigaito M. Cationic RAFT Polymerization Using ppm Concentrations of Organic Acid. Angew Chem Int Ed. 2015;54:1924–8. https://doi.org/10.1002/anie.201410858
Ramozzi R, Morokuma K. Revisiting the passerini reaction mechanism: existence of the nitrilium, organocatalysis of its formation, and solvent effect. J Org Chem. 2015;80:5652–7. https://doi.org/10.1021/acs.joc.5b00594
Maeda S, Komagawa S, Uchiyama M, Morokuma K. Finding reaction pathways for multicomponent reactions: the passerini reaction is a four-component reaction. Angew Chem Int Ed. 2011;50:644–9. https://doi.org/10.1002/anie.201005336
Sarri P, Venturi F, Cuda F, Roelens S. Binding of acetylcholine and tetramethylammonium to flexible cyclophane receptors: improving on binding ability by optimizing host’s geometry. J Org Chem. 2004;69:3654–61. https://doi.org/10.1021/jo049899j
Loim NM, Kelbyscheva ES. Synthesis of dendrimers with terminal formyl groups. Russ Chem Bull 2004;53:2080–5. https://doi.org/10.1007/s11172-005-0076-z
RK gratefully acknowledges the Leading Initiative for Excellent Young Researchers (LEADER) and a Grant-in-Aid for Scientific Research (C) (no. 19K05578) for financial support.
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Kakuchi, R., Okura, Y. The Passerini three-component reaction of aldehyde end-functionalized polymers via RAFT polymerization using chain transfer agents featuring aldehyde. Polym J 52, 1057–1066 (2020). https://doi.org/10.1038/s41428-020-0368-z
Analytical Chemistry (2020)