Following Sharpless' visionary characterization of several idealized reactions as click reactions, the materials science and synthetic chemistry communities have pursued numerous routes toward the identification and implementation of these click reactions. Herein, we review the radical-mediated thiol-ene reaction as one such click reaction. This 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. Further, the thiol-ene reaction is most frequently photoinitiated, particularly for photopolymerizations resulting in highly uniform polymer networks, promoting unique capabilities related to spatial and temporal control of the click reaction. The reaction mechanism and its implementation in various synthetic methodologies, biofunctionalization, surface and polymer modification, and polymerization are all reviewed.

Thiol–Ene Click Chemistry

Current status and future perspectives in atom transfer radical polymerization (ATRP) are presented. Special emphasis is placed on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP. New hybrid materials based on organic/inorganic systems and natural/synthetic polymers are presented. Some current and forthcoming applications are described.

Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives

The merits of thiol-click chemistry and its potential for making new forays into chemical synthesis and materials applications are described Since thiols react to high yields under benign conditions with a vast range of chemical species, their utility extends to a large number of applications in the chemical, biological, physical, materials and engineering fields This critical review provides insight into emerging venues for application as well as new mechanistic understanding of this exceptional chemistry in its many forms (81 references)

Thiol-click chemistry: a multifaceted toolbox for small molecule and polymer synthesis

Department of Chemistry, Department of Radiology, Washington University in Saint Louis, Saint Louis, Missouri 63130, Department of Chemistry, Texas A&M University, College Station, Texas 77842, Cancer Center Karolinska, Department of Oncology-Pathology CCK, R8:03 Karolinska Hospital and Institute, SE-171 76 Stockholm, Sweden, and Department of Chemistry and Biochemistry, Department of Materials, and Materials Research Laboratory, University of California, Santa Barbara, California 93106

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Applications of Orthogonal “Click” Chemistries in the Synthesis of Functional Soft Materials

Thiol-ene “click” reactions and recent applications in polymer and materials synthesis

The photopolymerization of mixtures of multifunctional thiols and enes is an efficient method for the rapid production of films and thermoset plastics with unprecedented physical and mechanical properties. One of the major obstacles in traditional free-radical photopolymerization is essentially eliminated in thiol–ene polymerizations because the polymerization occurs in air almost as rapidly as in an inert atmosphere. Virtually any type of ene will participate in a free-radical polymerization process with a multifunctional thiol. Hence, it is possible to tailor materials with virtually any combination of properties required for a particular application. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5301–5338, 2004

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/pola.20366

Thiol–enes: Chemistry of the past with promise for the future

Photoinduced frontal polymerization was performed on a variety of multifunctional (meth)acrylates, and evaluation of the effect of monomer structure on the ability to sustain a traveling front was made. Photo-DSC was used to measure the photopolymerization rate of each monomer at 25 °C. The results were correlated with their ability to initiate and sustain a traveling front polymerization. The start time and the front velocity of each (meth)acrylate that could initiate/sustain a front photolytically were measured. The results clearly demonstrate that the molecular weight per double bond is directly related to the front velocity. Trimethylolpropane triacrylate (TMPTA), which exhibited the fastest front velocity, was evaluated in depth to determine the effect of varying the photoinitiator and thermal initiator on the frontal polymerization rate. When a multifunctional thiol was added to TMPTA, the start time was dramatically reduced and the velocity increased for low thiol concentrations. However, the veloc...

UV-Induced Frontal Polymerization of Multifunctional (Meth)acrylates

The relationship between the photopolymerization rate of hydroxyalkyl acrylates and their structure has been investigated. The polymerization rates of hydroxyalkyl acrylates are significantly higher than those observed for typical monofunctional acrylate monomers and rival those of multifunctional monomers. By polymerizing at several temperatures, it was shown that the enhanced rates are directly proportional to the degree of hydrogen bonding. Apparently, termination rates are greatly reduced by hydrogen bonding, which is present in both the unpolymerized monomer and the final polymer film.

Influence of Hydrogen Bonding on Photopolymerization Rate of Hydroxyalkyl Acrylates

The effect of the chemical structure on the reactivity of alkenes used in thiol–ene photopolymerizations has been investigated with real-time infrared spectroscopy. Model studies of thiol–ene photoreactions with various monofunctional hydrocarbon alkenes and the monofunctional thiol ethyl-3-mercaptopropionate have been performed to identify and understand structure–reactivity relationships. The results demonstrate that terminal enes react very rapidly with thiol, achieve complete conversion, and are independent of the aliphatic hydrocarbon substituent length. Disubstitution on a single carbon of a terminal ene significantly reduces the reactivity, whereas substitution on the carbon α to the terminal ene has a minimal influence on the reactivity. Internal trans enes display reduced reactivity and a lower overall conversion and deviate from the standard thiol–ene reaction mechanism because of steric strain induced by 1,3-interactions. The reactivity and conversion of internal trans enes decrease as the substituents on the ene become larger, reaching a minimum when the substituent size is greater than or equal to that of propyl groups. Internal cis enes react rapidly with thiol; however, they undergo a fast isomerization–elimination reaction sequence generating the trans ene, which proceeds to react at a reduced rate with thiol. The reactivity of cyclic enes is dictated by ring strain, stereoelectronic effects, and hydrogen abstractability. The reactivity trends in the model studies have been used to explain the photopolymerization mechanism and kinetics of a series of multifunctional thiol–ene systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6283–6298, 2004

Todd M. Roper

Papers

Thiol–enes: Chemistry of the past with promise for the future

UV-Induced Frontal Polymerization of Multifunctional (Meth)acrylates

Influence of Hydrogen Bonding on Photopolymerization Rate of Hydroxyalkyl Acrylates

Influence of the alkene structure on the mechanism and kinetics of thiol–alkene photopolymerizations with real‐time infrared spectroscopy

The kinetics of vinyl acrylate photopolymerization