Abstract
Developments and progress in polymer science are often inspired by organic chemistry. In recent years, multicomponent reactions—especially the Passerini and Ugi reactions—have become very important tools for macromolecular design, mainly due to their modular character. In this review, the versatility of the Passerini and Ugi reactions in polymer science is highlighted by discussing recent examples of their use for monomer synthesis, as polymerization techniques, and for postpolymerization modification, as well as their suitability for architecture control, sequence control, and sequence definition.
Similar content being viewed by others
References
Zhu J, Bienaymé H (2006) Multicomponent reactions. John Wiley, New Jersey
Zhu J, Wang Q, Wang M (2014) Multicomponent reactions in organic synthesis. John Wiley, New Jersey
Strecker A (1850) Liebigs Ann Chem 75:25
Strecker A (1854) Ueber einen neuen aus Aldehyd-Ammoniak und Blausäure entstehenden Körper. Justus Liebigs Annalen der Chemie 91:349
Passerini M (1921) Isonitriles. II. Compounds with aldehydes or with ketones and monobasic organic acids. Gazz Chim Ital 51:181
Ugi I (1959) Versuche mit Isonitrilen. Angew Chem Int Ed 71:386
Passerini M, Simone L (1921) Sopra gli isonitrili (I). Composto del p-isonitril-azobenzolo con acetone ed acido acetico. Gazz Chim 51:126
Ugi I, Steinbrückner C (1960) Über ein neues Kondensations-Prinzip. Angew Chem 72:267
Mumm O (1910) Umsetzung von Säureimidchloriden mit Salzen organischer Säuren und mit Cyankalium. Ber Dtsch Chem Ges 43:886
Kreye O, Tóth T, Meier MAR (2011) Introducing multicomponent reactions to polymer science: Passerini reactions of renewable monomers. J Am Chem Soc 133:1790
Jiang X, Feng C, Lu G, Huang X (2015) Application of named reactions in polymer synthesis. Sci China Chem 58:1695
Yang B, Zhao Y, Wei Y, Fu C, Tao L (2015) The Ugi reaction in polymer chemistry: syntheses, applications and perspectives. Polym Chem 6:8233
Sehlinger A, Meier MAR (2015) In: Theato P (ed) Multi-component and sequential reactions in polymer synthesis. Springer International, Cham, p 61
Kakuchi R (2014) Multicomponent reactions in polymer synthesis. Angew Chem Int Ed 53:46
Rubinshtein M, James CR, Young JL, Ma YJ, Kobayashi Y, Gianneschi NC, Yang J (2010) Facile procedure for generating side chain functionalized poly(α-hydroxy acid) copolymers from aldehydes via a versatile Passerini-type condensation. Org Lett 12:3560
Kreye O, Trefzger C, Sehlinger A, Meier MAR (2014) Multicomponent reactions with a convertible isocyanide: efficient and versatile grafting of ADMET-derived polymers. Macromol Chem Phys 215:2207
Sehlinger A, de Espinosa LM, Meier MAR (2013) Synthesis of diverse asymmetric α,ω-dienes via the Passerini three-component reaction for head-to-tail ADMET polymerization. Macromol Chem Phys 214:2821
Sehlinger A, Kreye O, Meier MAR (2013) Tunable polymers obtained from Passerini multicomponent reaction derived acrylate monomers. Macromolecules 46:6031
Schmidt S, Koldevitz M, Noy J-M, Roth PJ (2015) Multicomponent isocyanide-based synthesis of reactive styrenic and (meth)acrylic monomers and their RAFT (co)polymerization. Polym Chem 6:44
Noy J-M, Koldevitz M, Roth PJ (2015) Thiol-reactive functional poly(meth)acrylates: multicomponent monomer synthesis, RAFT (co)polymerization and highly efficient thiol-para-fluoro postpolymerization modification. Polym Chem 6:436
Pei Y, Noy J-M, Roth PJ, Lowe AB (2015) Thiol-reactive Passerini-methacrylates and polymorphic surface functional soft matter nanoparticles via ethanolic RAFT dispersion polymerization and post-synthesis modification. Polym Chem 6:1928
Pei Y, Dharsana NC, van Hensbergen JA, Burford RP, Roth PJ, Lowe AB (2014) RAFT dispersion polymerization of 3-phenylpropyl methacrylate with poly[2-(dimethylamino)ethyl methacrylate] macro-CTAs in ethanol and associated thermoreversible polymorphism. Soft Matter 10:5787
von Czapiewski M, Kreye O, Mutlu H, Meier MAR (2013) Cross-metathesis versus palladium-catalyzed C-H activation: Acetoxy ester functionalization of unsaturated fatty acid methyl esters. Eur J Lipid Sci Technol 115:76
von Czapiewski M, Gugau K, Todorovic L, Meier MAR (2016) Synthesis of polyacrylates from limonene by catalytic oxidation and multi-component reaction. Eur Polym J 83:359
Sabitha G, Nayak S, Bhikshapathi M, Yadav JS (2011) Palladium hydroxide catalyzed isomerization of primary allylic alcohols to aldehydes: application to the formal synthesis of (−)-Brevisamide. Org Lett 13:382
Sehlinger A, Ochsenreither K, Bartnick N, Meier MAR (2015) Potentially biocompatible polyacrylamides derived by the Ugi four-component reaction. Eur Polym J 65:313
Galperin A, Long TJ, Ratner BD (2010) Degradable, thermo-sensitive poly(N-isopropyl acrylamide)-based scaffolds with controlled porosity for tissue engineering applications. Biomacromolecules 11:2583
Kawaguchi H (2014) Thermoresponsive microhydrogels: preparation, properties and applications. Polym Int 63:925
Vignaud T, Ennomani H, Théry M (2014) Polyacrylamide hydrogel micropatterning. Methods Cell Biol 120:93
Algi MP, Okay O (2014) Highly stretchable self-healing poly(N,N-dimethylacrylamide) hydrogels. Eur Polym J 59:113
Kienberger J, Kreutzwiesner E, Noormofidi N, Klarholz I, Harms C, Slugovc C (2012) Towards the antimicrobial finishing of poly(isoprene). Macromol Symposia 311:98
Kienberger J, Noormofidi N, Mühlbacher I, Klarholz I, Harms C, Slugovc C (2012) Antimicrobial equipment of poly(isoprene) applying thiol-ene chemistry. J Polym Sci 50:2236
Deng X-X, Li L, Li Z-L, Lv A, Du F-S, Li Z-C (2012) Sequence regulated poly(ester-amide)s based on Passerini reaction. ACS Macro Lett 1:1300
Wang Y-Z, Deng X-X, Li L, Li Z-L, Du F-S, Li Z-C (2013) One-pot synthesis of polyamides with various functional side groups via Passerini reaction. Polym Chem 4:444
Zhang L-J, Deng X-X, Du F-S, Li Z-C (2013) Chemical synthesis of functional poly(4-hydroxybutyrate) with controlled degradation via intramolecular cyclization. Macromolecules 46:9554
Sehlinger A, Schneider R, Meier MAR (2014) Passerini addition polymerization of an AB-type monomer—a convenient route to versatile polyesters. Eur Polym J 50:150
Zhang J, Zhang M, Du F-S, Li Z-C (2016) Synthesis of functional polycaprolactones via Passerini multicomponent polymerization of 6-oxohexanoic acid and isocyanides. Macromolecules 49:2592
Lin W, Guan X, Sun T, Huang Y, Jing X, Xie Z (2015) Reduction-sensitive amphiphilic copolymers made via multi-component Passerini reaction for drug delivery. Colloids Surf 126:217
Sehlinger A, Dannecker P-K, Kreye O, Meier MAR (2014) Diversely substituted polyamides: macromolecular design using the Ugi four-component reaction. Macromolecules 47:2774
Sehlinger A, Schneider R, Meier MA (2014) Ugi reactions with CO2: access to functionalized polyurethanes, polycarbonates, polyamides, and polyhydantoins. Macromol Rapid Commun 35:1866
Gangloff N, Nahm D, Döring L, Kuckling D, Luxenhofer R (2015) Polymerization via the Ugi-reaction using aromatic monomers. J Polym Sci 53:1680
Hartweg M, Becer CR (2016) Direct polymerization of levulinic acid via Ugi multicomponent reaction. Green Chem 18:3272
Zhang X, Wang S, Liu J, Xie Z, Luan S, Xiao C, Tao Y, Wang X (2016) Ugi reaction of natural amino acids: a general route toward facile synthesis of polypeptoids for bioapplications. ACS Macro Lett 5:1049
Kreye O, Kugele D, Faust L, Meier MAR (2014) Divergent dendrimer synthesis via the Passerini three-component reaction and olefin cross-metathesis. Macromol Rapid Commun 35:317
Deng X-X, Du F-S, Li Z-C (2014) Combination of orthogonal ABB and ABC multicomponent reactions toward efficient divergent synthesis of dendrimers with structural diversity. ACS Macro Lett 3:667
Wessjohann L, Henze M, Kreye O, Rivera D (2013) WO Patent 134,607, 2011. European Patent 2563847
Jee J-A, Spagnuolo LA, Rudick JG (2012) Convergent synthesis of dendrimers via the Passerini three-component reaction. Org Lett 14:3292
Jee J-A, Song S, Rudick JG (2015) Enhanced reactivity of dendrons in the Passerini three-component reaction. Chem Commun 51:5456
Deng X-X, Cui Y, Wang Y-Z, Du F-S, Li Z-C (2014) Graft copolymers with polyamide backbones via combination of Passerini multicomponent polymerization and controlled chain-growth polymerization. Aust J Chem 67:555
Li L, Kan X-W, Deng X-X, Song C-C, Du F-S, Li Z-C (2013) Simultaneous dual end-functionalization of PEG via the Passerini three-component reaction for the synthesis of ABC miktoarm terpolymers. J Polym Sci 51:865
Oelmann S, Solleder SC, Meier MAR (2016) Controlling molecular weight and polymer architecture during the Passerini three component step-growth polymerization. Polym Chem 7:1857
Mutlu H, Lutz J-F (2014) Reading polymers: sequencing of natural and synthetic macromolecules. Angew Chem Int Ed 53:13010
Badi N, Lutz J-F (2009) Sequence control in polymer synthesis. Chem Soc Rev 38:3383
Qu C, He J (2015) Recent developments in the synthesis of sequence controlled polymers. Sci China Chem 58:1651
Colquhoun H, Lutz J-F (2014) Information-containing macromolecules. Nat Chem 6:455
Hartmann L, Häfele S, Peschka-Süss R, Antonietti M, Börner HG (2008) Tailor-made poly(amidoamine)s for controlled complexation and condensation of DNA. Chemistry 14:2025
Terashima T, Mes T, De Greef TFA, Gillissen MAJ, Besenius P, Palmans ARA, Meijer EW (2011) Single-chain folding of polymers for catalytic systems in water. J Am Chem Soc 133:4742
Yang L, Zhang Z, Cheng B, You Y, Wu D, Hong C (2015) Two tandem multicomponent reactions for the synthesis of sequence-defined polymers. Sci China Chem 58:1734
Solleder SC, Meier MAR (2014) Sequence control in polymer chemistry through the Passerini three-component reaction. Angew Chem Int Ed 53:711
Solleder SC, Wetzel KS, Meier MAR (2015) Dual side chain control in the synthesis of novel sequence-defined oligomers through the Ugi four-component reaction. Polym Chem 6:3201
Solleder SC, Zengel D, Wetzel KS, Meier MAR (2016) A scalable and high-yield strategy for the synthesis of sequence-defined macromolecules. Angew Chem Int Ed 55:1204
Sehlinger A, Verbraeken B, Meier MAR, Hoogenboom R (2015) Versatile side chain modification via isocyanide-based multicomponent reactions: tuning the LCST of poly(2-oxazoline)s. Polym Chem 6:3828
Xue L, Xiong X, Chen K, Luan Y, Chen G, Chen H (2016) Modular synthesis of glycopolymers with well-defined sugar units in the side chain via Ugi reaction and click chemistry: hetero vs. homo. Polym Chem 7:4263
Yang B, Zhao Y, Fu C, Zhu C, Zhang Y, Wang S, Wei Y, Tao L (2014) Introducing the Ugi reaction into polymer chemistry as a green click reaction to prepare middle-functional block copolymers. Polym Chem 5:2704
Wu H, Yang B, Zhao Y, Wei Y, Wang Z, Wang X, Tao L (2016) Fluorescent protein-reactive polymers via one-pot combination of the Ugi reaction and RAFT polymerization. Polym Chem 7:4867
Author information
Authors and Affiliations
Corresponding author
Additional information
This article is part of the Topical Collection “Polymer Synthesis Based on Triple-bond Building Blocks”; edited by Ben Zhong Tang, Rongrong Hu.
Rights and permissions
About this article
Cite this article
Llevot, A., Boukis, A.C., Oelmann, S. et al. An Update on Isocyanide-Based Multicomponent Reactions in Polymer Science. Top Curr Chem (Z) 375, 66 (2017). https://doi.org/10.1007/s41061-017-0153-4
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s41061-017-0153-4