Revisiting thiol‐yne chemistry: Selective and efficient monoaddition for block and graft copolymer formation

  title={Revisiting thiol‐yne chemistry: Selective and efficient monoaddition for block and graft copolymer formation},
  author={Johannes K. Sprafke and Jason M. Spruell and Kaila M. Mattson and Damien Montarnal and Alaina J. McGrath and Robert P{\"o}tzsch and Daigo Miyajima and Jerry G. Hu and Allegra A. Latimer and Brigitte Voit and Takuzo Aida and Craig J. Hawker},
  journal={Journal of Polymer Science Part A},
The untapped potential of radical thiol-yne mono-addition chemistry is exploited to overcome the known limitations of thiol-ene chemistry in polymer coupling and block copolymer formation. By careful choice of alkyne, the reaction can selectively lead to the mono-addition product with efficiencies surpassing those achieved by traditional thiol-ene chemistry. This improvement is illustrated by the nearly quantitative synthesis of a variety of diblock and graft copolymers. © 2014 Wiley… 
Visible Light Photocatalytic Thiol–Ene Reaction: An Elegant Approach for Fast Polymer Postfunctionalization and Step-Growth Polymerization
An elegant approach for fast polymer postfunctionalization and step-growth polymerization (via addition reaction) under aerobic condition was developed from visible light photocatalytic thiol–ene
Multi-Functional Hyperbranched Poly(vinylene sulfide)s Constructed via Spontaneous Thiol–Yne Click Polymerization
Multifunctional hyperbranched polymers have found wide applications in diverse areas. However, the preparation of these polymers is generally under harsh polymerization conditions with limited
Synthesis of three-dimensional porous hyper-crosslinked polymers via thiol–yne reaction
The syntheses of two porous hyper-crosslinked polymers via thiol–yne reaction with rigid tetrahedral and pseudo-octahedral core structures showed a high thermal stability as well as insolubility in common organic solvents.
Heterofunctional RAFT-derived PNIPAM via cascade trithiocarbonate removal and thiol-yne coupling click reaction
An efficient one-pot process to functionalize the α- and ω-positions of RAFT-derived poly(N-isopropylacrylamide) (PNIPAM) by two inherently different mechanistic pathways is reported. The method
Star polymers by photoinduced copper-catalyzed azide–alkyne cycloaddition click chemistry
Well-defined star polymers consisting of tri-, tetra-, or octa-arms have been prepared via coupling-onto strategy using photoinduced copper(I)-catalyzed 1,3-dipolar cycloaddition click reaction. An
Structural Versatility in Slide‐Ring Gels: Influence of Co‐Threaded Cyclodextrin Spacers
A one-pot strategy for the fabrication of novel slide-ring (SR) gels based on supramolecular polyrotaxane structures with cyclodextrin-derived cross-links and additional free cyclodeXTrin ring spacers co-threaded onto the polymer backbones controlled by adjusting the feed ratio of the starting materials.
Efficient Thiol–Yne Click Chemistry of Redox-Active Ethynylferrocene
The application of ethynylferrocene, FcC≡CH (1), as a highly efficient electroactive precursor for the thiol–yne click reaction is presented. For this purpose, a wide range of functionalized thiols,
Click Chemistry in Macromolecular Design: Complex Architectures from Functional Polymers
This contribution reviews the applications of click chemistry reactions in design and synthesis of various macromolecular architectures that hold key aspects in polymer science. By considering the
Efficient Metal-Free “Grafting Onto” Method for Bottlebrush Polymers by Combining RAFT and Triazolinedione–Diene Click Reaction
An efficient metal-free “grafting onto” method was developed for preparing bottlebrush polymers based on the combination of reversible addition–fragmentation chain transfer polymerization (RAFT) and
Polymer Coupling via Hetero-Disulfide Exchange and Its Applications to Rewritable Polymer Brushes.
The metal-free synthetic procedure, accessibility to patterned brushes, and switchable surface properties via the writing-erasing-rewriting process are attractive features of the present approach.


Facile synthesis of dendrimers combining aza-Michael addition with Thiol-yne click chemistry
A highly efficient approach to prepare dendrimers by taking advantage of the orthogonal characteristic of aza-Michael addition and thiol-yne reactions is reported, which can be used for selective and specific conjugation with various functional groups.
Hyperbranched polymers by thiol-yne chemistry: from small molecules to functional polymers.
This work demonstrates how the thiol-yne reaction can be used to form hyperbranched polymers from both small organic molecules and polymeric chains bearing an alkyne and a thiol.
The power of thiol‐ene chemistry
As a tribute to Professor Charlie Hoyle, we take the opportunity to review the impact of thiol-ene chemistry on polymer and materials science over the past 5 years. During this time, a renaissance in
Robust, efficient, and orthogonal synthesis of dendrimers via thiol-ene "click" chemistry.
Dendrimers up to the fourth generation were successfully prepared via the divergent growth strategy using a combination of thiol-ene "click" chemistry and traditional esterification reactions to functionalize with carboxylic acid, pyrene, and Fmoc-protected cysteine moieties via thiol -ene reactions.
Thiol-ene click chemistry.
The radical-mediated thiol-ene reaction has all the desirable features of a click reaction, being highly efficient, simple to execute with no side products and proceeding rapidly to high yield.
Diblock Copolymers as Scaffolds for Efficient Functionalization via Click Chemistry
A set of different alkyne containing diblock copolymers based on 4-hydroxystyrene was synthesized by nitroxide mediated radical polymerization (NMRP), all with excellent control over the molecular
Thiol-yne click chemistry: A powerful and versatile methodology for materials synthesis
Radical mediated thiol-yne polymerization reactions complement the more well-known thiol-ene radical polymerization processes, with the added advantage of increased functionality. In one system
Thiol-click chemistry: a multifaceted toolbox for small molecule and polymer synthesis.
This critical review provides insight into emerging venues for application as well as new mechanistic understanding of this exceptional chemistry in its many forms.
Rapid Synthesis of Block and Cyclic Copolymers via Click Chemistry in the Presence of Copper Nanoparticles.
A new method for the rapid and efficient coupling of homopolymers to yield di- and triblock copolymers as well as cyclic polymers using the 3 + 2 π Huisgen copper catalyzed cyclo-addition reaction
Photo‐initiated thiol–ene “click” hydrogels from RAFT‐synthesized poly(N‐isopropylacrylamide)
Despite the efficiency and robustness of the widely used copper-catalyzed 1,3-dipolar cycloaddition reaction, the use of copper as a catalyst is often not attractive, particularly for materials