Piers-Rubinsztajn Reaction Research Articles

Reduction Polymerization of CO2 with Phenylene Silanes Catalyzed by Single Component B(C6F5)3.

CO2 is an abundant C1 resource but a green-house gas and chemically inert. Thus, its utilization has been a promising but challenging project. Herein, we report the unprecedented polymerization of CO2 and C6H4(SiMe2H)2 using B(C6F5)3 alone under mild conditions to give poly(silphenylene siloxane) accompanied by releasing CH4. The copolymerization can be extended to comonomers of phenylene silanes bearing functional groups. Moreover, it combines with Piers-Rubinsztajn reaction to establish a tandem polymerization system to achieve super thermal resistant poly(siloxane-co-silphenylene siloxane)s. Density functional theory reveals that B(C6F5)3 is activated by silanes to form free HB(C6F5)2, which is the true active species for CO2 reducing to borylformate, the rate controlling step of the polymerization procedure. The subsequent multiple reductions of borylformate to CH4 and the step-growth to poly(silphenylene siloxane)s can be fulfilled by both B(C6F5)3 and HB(C6F5)2, and the former shows a slightly higher activity. This work opens a new avenue of utilizing CO2 to fabricate polysiloxanes that is unable to access using current manners.

Piers-Rubinsztajn reaction to unlock an 8-step synthesis of 7-hydroxy cannabidiol.

A scalable synthesis of 7-hydroxy cannabidiol (7-OH CBD), a primary metabolite of (-)-cannabidiol (CBD), is highly desirable, from an industrial point of view, to enable future clinical trials. A Piers-Rubinsztajn reaction was key to enable a mild deprotection and a concise synthesis of 7-OH CBD from commercially available CBD, in 31% overall yield.

13-8-13-Membered Tricyclic Ladder-Type Siloxanes Hybridized with BINOLs: Synthesis, Characterization, and Fluorescence Sensing of Fluorides.

Developing fluorescent chemosensors with sensitivity and high specificity for recognizing fluorides is still challenging. Herein, four innovative compounds based on 13-8-13-membered tricyclic ladder-type siloxanes hybridized with BINOLs (abbreviated as TLS-BINOLs) were prepared through the B(C6F5)3-catalyzed Piers-Rubinsztajn reaction. The well-defined ladder-type structure of the TLS-BINOLs was determined by X-ray crystallographic analysis. Additionally, the fluorescent sensing ability of the TLS-BINOLs toward anions was studied. Our finding revealed that all four ladder-type compounds (TLS-BINOLs) exhibited high specificity in recognizing fluorides through fluoride-triggered structural decomposition. The detection limits for fluorides were determined to be 0.37, 0.35, 0.39, and 0.48 μM for the respective TLS-BINOLs. The nonemissive product induced by the fluorides was also determined using single-crystal X-ray diffraction analysis.

Tris(pentafluorophenyl)borane-catalyzed Hydride Transfer Reactions in Polysiloxane Chemistry-Piers-Rubinsztajn Reaction and Related Processes.

Tris(pentafluorophenyl)borane (TPFPB) is a unique Lewis acid that catalyzes the condensation between hydrosilanes (Si-H) and alkoxysilanes (Si-OR), leading to the formation of siloxane bonds (Si-OSi) with the release of hydrocarbon (R-H) as a byproduct-the so-called Piers-Rubinsztajn reaction. The analogous reactions of hydrosilanes with silanols (Si-OH), alcohols (R-OH), ethers (R-OR') or water in the presence of TPFPB leads to the formation of a siloxane bond, alkoxysilane (Si-OR or Si-OR') or silanol (Si-OH), respectively. The above processes, often referred to as Piers-Rubinsztajn reactions, provide new synthetic tools for the controlled synthesis of siloxane materials under mild conditions with high yields. The common feature of these reactions is the TPFPB-mediated hydride transfer from silicon to carbon or hydrogen. This review presents a summary of 20 years of research efforts related to this field, with a focus on new synthetic methodologies leading to numerous previously difficult to synthesize well-defined siloxane oligomers, polymers and copolymers of a complex structure and potential applications of these new materials. In addition, the mechanistic aspects of the recently discovered reactions involving hydride transfer from silicon to silicon are discussed in more detail.

Synthesis and characterization of sulfide/sulfone-containing 18-8-18-membered-ring ladder-type siloxanes.

Innovative macrocyclic 14-membered molecule (5) and tricyclic 18-8-18-membered-ring ladder-type siloxane-based compound (7), with sulfide units inserted in the backbone were prepared through B(C6F5)3-catalyzed Piers-Rubinsztajn reaction. Further oxidation of 5 and 7 with m-CPBA enables the synthesis of the novel sulfonyl-containing cyclic and ladder-type compound (8 and 9) in high yields. Both tricyclic ladder-type products (7 and 9) show superior thermostability and their well-defined syn-type structures were determined by X-ray crystallographic analysis. The compounds 7 and 9 may become promising building blocks for various new materials.

Chelating Silicone Dendrons: Trying to Impact Organisms by Disrupting Ions at Interfaces.

The viability of pathogens at interfaces can be disrupted by the presence of (cationic) charge and chelating groups. We report on the synthesis of silicone dendrimers and linear polymers based on a motif of hexadentate ligands with the ability to capture and deliver metal ions. Mono-, di- or trialkoxysilanes are converted in G1 to analogous vinylsilicones and then, iteratively using the Piers-Rubinsztajn reaction and hydrosilylation, each vinyl group is transformed into a trivinyl cluster at G2. The thiol-ene reaction with cysteamine or 3-mercaptopropionic acid and the trivinyl cluster leads to hexadentate ligands 3 × N–S or 3 × HOOC–S. The compounds were shown to effectively capture a variety of metals ions. Copper ion chelation was pursued in more detail, because of its toxicity. On average, metal ions form chelates with 2.4 of the three ligands in a cluster. Upon chelation, viscous oils are converted to (very) soft elastomers. Most of the ions could be stripped from the elastomers using aqueous EDTA solutions, demonstrating the ability of the silicones to both sequester and deliver ions. However, complete ion removal is not observed; at equilibrium, the silicones remain ionically crosslinked.

High Refractive Index, Enantiopure Silicones Based on BINOL.

The high refractive index aromatic compound, binaphthol (BINOL), is readily incorporated into silicone polymer chains using the Piers-Rubinsztajn (PR) reaction; alternating and random linear copolymers, and elastomers are available. The highest refractive index (RI) materials are BINOL rich. It is not possible to directly make high refractive index linear polymers with very short HSi-capped, telechelic silicone chains, as they do not react cleanly. However, chain extending short vinyl-capped BINOL macromers with simple arylsilanes using hydrosilylation leads to polymers with a molar mass of up to 8000 and refractive indices of up to 1.58. Elastomers are prepared using similar processes. The reactions are facile to practice and suggest BINOL can be harnessed in these and other processes to augment RI.

Facile construction of luminescent silicone elastomers from the compatibilization of porphyrins via the Piers-Rubinsztajn reaction

In this work, in order to improve the low solubility and expand the applications of porphyrins in polysiloxanes, a series of designed siloxane-modified porphyrin derivatives was fabricated based on the Piers-Rubinsztajn reaction. The solubility of the porphyrin derivatives in polysiloxanes could be controlled by adjusting the siloxane chain length. Furthermore, the silicone-modified porphyrin derivatives were doped into a silicone elastomer prepolymer to obtain luminescent elastomers, which also showed good transparency and interfacial stability. In addition, the thermal stability and mechanical properties were well preserved compared with the original elastomer. Finally, based on the above-mentioned properties, an organosilicon elastomer doped with porphyrin showed good processability and plasticity, and could be fabricated into various complex three-dimensional models.

Main Group Catalysis: Cationic Si(II) and Ge(II) Compounds as Catalysts in Organosilicon Chemistry

Cyclopentadienyl (Cp)-coordinated cationic Si(II) (1) and Ge(II) compounds (2) are a new class of catalysts for various transformations in organosilicon chemistry. This review demonstrates that these compounds effectively catalyze technically important reactions, such as the hydrosilylation of carbon-carbon multiple bonds and various types of siloxane-coupling reactions, e.g., the Piers-Rubinsztajn reaction and the oxidative siloxane coupling reaction. Whereas the cationic Si(II) compounds are sensitive to air and moisture, the corresponding cationic Ge(II) compounds are bench stable, thus offering further advantages. The new catalysts contribute to the growing need for the substitution of transition metals and heavier main group metals by their lighter congeners, especially in industrially relevant organosilicon chemistry.

Facile construction of aggregation-induced emission molecular liquids via Piers-Rubinsztajn reaction for green fluorescent ink

Solvent-free luminescent molecular liquids (LMLs), which exhibit nonvolatile fluidic nature and active optoelectronic properties, were widely used. For further development, we introduced siloxane units into AIE molecules, designed and synthesized TPE derivatives with siloxane side chains via facile Piers-Rubinsztajn reaction. The obtained AIE molecular liquids exhibit unique photophysical properties. Compared with the obtained alkyl TPE-solids, siloxane TPE show liquid state, which proves that the siloxane units have stronger liquefaction effect than alkyl. Viscosity test shows that siloxane TPE-liquids has far more lower viscosity and better fluidity than the long-chain alkyl molecular liquids in previous research. All those properties are attributed to the weak interaction between flexible molecular chains of siloxane. Besides, fluorescence test shows temperature responsiveness of siloxane TPE-liquids. We developed this low-viscosity nonvolatile AIE molecular liquid as green fluorescent ink.

Vinyl-Functionalized Janus Ring Siloxane: Potential Precursors to Hybrid Functional Materials.

A vinyl-functionalized all-cis-tetrasiloxycyclotetrasiloxane [ViSi(OSiMe2H)O]4 (Vi = vinyl group) Janus precursor was prepared from potassium cyclotetrasiloxane silanolate. The Janus precursor was selectively modified at its dimethylhydrosilyl groups [–SiMe2H] via the Piers–Rubinsztajn reaction to obtain a family of new tetravinyl-substituted Janus rings [ViSi(OR’)O]4 containing various functional groups in moderate yields. Remarkably, the tetravinyl groups on the structure remained intact after modification by the Piers–Rubinsztajn reaction. Since these synthesized compounds possess multiple functional groups (up to eight per molecule), they are potential precursors for advanced hybrid organic-inorganic functional materials.

Spatially Controlled Highly Branched Vinylsilicones.

Branched silicones possess interesting properties as oils, including their viscoelastic behavior, or as precursors to controlled networks. However, highly branched silicone polymers are difficult to form reliably using a “grafting to” strategy because functional groups may be bunched together preventing complete conversion for steric reasons. We report the synthesis of vinyl-functional highly branched silicone polymers based, at their core, on the ability to spatially locate functional vinyl groups along a silicone backbone at the desired frequency. Macromonomers were created and then polymerized using the Piers–Rubinsztajn reaction with dialkoxyvinylsilanes and telechelic HSi-silicones; molecular weights of the polymerized macromonomers were controlled by the ratio of the two reagents. The vinyl groups were subjected to iterative (two steps, one pot) hydrosilylation with alkoxysilane and Piers–Rubinsztajn reactions, leading to high molecular weight, highly branched silicones after one or two iterations. The vinyl-functional products can optionally be converted to phenyl/methyl-modified branched oils or elastomers.

Dumbbell‐Shaped, Graft and Bottlebrush Polymers with All‐Siloxane Nature: Synthetic Methodology, Thermal, and Rheological Behavior

Back Cover: In article number 2000645 by Ashot V. Arzumanyan and co-workers, a methodology for synthesizing dumbbell-shaped, graft and bottlebrush polymers with all-siloxane nature is suggested. They are synthesized from different generations and structure dendritic siloxanols and polyhydride-siloxanes by the Piers–Rubinsztajn reaction. The product physical properties are determined not only by the macromolecular structure, the linear chain length, the size and frequency of branched pendant, but also by the type of peripheral pendant substituents: Me or Et.

Transparent silphenylene elastomers from highly branched monomers

Catalyst free crosslinking of highly branched silphenylene monomers, made using the Piers–Rubinsztajn reaction, leads to high refractive index, soft elastomers.

Benzocyclobutene-functionalized hyperbranched polysiloxane for low-k materials with good thermostability

ABSTRACT Although hyperbranched polysiloxanes have been extensively studied, they have limited practical applications because of their low glass transition temperatures. In this study, we synthesized benzocyclobutene-functionalized hyperbranched polysiloxane (HB-BCB) via the Piers-Rubinsztajn reaction. The synthesized material was cured and crosslinking occurred at temperatures greater than 200 °C, forming a low-k thermoset resin with high thermostability. The structure of the resin was characterized using nuclear magnetic resonance (NMR) spectroscopy, viz. 1H NMR and 13C NMR spectroscopy. 29Si NMR spectroscopy was used to calculate the degree of branching. Differential scanning calorimetry, dynamic mechanical analysis, and thermogravimetric analysis revealed that the cured resin possesses good high-temperature mechanical properties and exhibits a high thermal decomposition temperature (Td5 = 512 °C). In addition, the cured resin has a low dielectric constant (k = 2.70 at 1 MHz) and low dissipation factor (2.13 × 10−3 at 1 MHz). Thus, the prepared resin can function as a low-k material with excellent high-temperature performance. These findings indicate that the performance of crosslinked siloxane is significantly attributed to the introduction of BCB groups and the formation of the highly crosslinked structure.

Influence of the tetraalkoxysilane crosslinker on the properties of polysiloxane-based elastomers prepared by the Lewis acid-catalysed Piers-Rubinsztajn reaction

We investigate the influence of the tetrafunctional alkoxysilan R-groups, with a range of sterics and electronics. This is through a solvent free polysiloxane network formation under ambient conditions using Lewis acid catalysed Piers-Rubinsztajn (PR) reaction.

Facile fabrication of eugenol-containing polysiloxane films with good optical properties and excellent thermal stabilityviaSi–H chemistry

Biomass-containing polysiloxane films that exhibit good optical properties and excellent thermal stability for encapsulation have been developedviathe Piers–Rubinsztajn reaction and Pt-catalysed hydrosilylation.

Dumbbell-Shaped, Graft and Bottlebrush Polymers with All-Siloxane Nature: Synthetic Methodology, Thermal, and Rheological Behavior.

A methodology for synthesizing a wide range of dumbbell-shaped, graft and bottlebrush polymers with all-siloxane nature (without carbosilane linkers) is suggested. These macroarchitectures are synthesized from SiOH-containing compounds-silanol (Et3 SiOH) and siloxanol dendrons of the first and second generations, with various peripheral substituents (Me or Et)-and from linear siloxanes comprising terminal and internal SiH groups by the Piers-Rubinsztajn reaction. Products and key building blocks are obtained in yields up to 95%. These polymers are heat and frost-resistant siloxanes. As it turns out, the product physical properties are determined not only by the macromolecular structure, the linear chain length, the size and frequency of branched pendant, but also by the type of peripheral substituents-Me or Et-in the pendant. Thus, the viscosity of the graft polymers with branched pendant groups comprising peripheral Me-groups is more than ≈3-5 fold lower than that of analogous polymers with peripheral Et-groups.

A Fluorinated Thermocrosslinkable Organosiloxane: A New Low-k Material at High Frequency with Low Water Uptake.

In order to obtain low-k material with good comprehensive properties, a trifluoromethyl-containing organosiloxane with thermocrosslinkable vinyl and benzocyclobutene groups is designed and synthesized through the Piers-Rubinsztajn reaction. After treating at high temperature, the organosiloxane changed to form a cross-linked polysiloxane (called as c-FSi-BCB). c-FSi-BCB exhibits good dielectric properties with dielectric constant (Dk ) of 2.60 and dielectric loss (Df ) of 1.49 × 10-3 at a high frequency of 5GHz. Importantly, c-FSi-BCB maintains such good dielectric properties and exhibits low water uptake of below 0.076%, even after immersing it in boiling water for 96 h. c-FSi-BCB also displays good thermostability with a 5% weight loss temperature (T5d ) of 453 °C. These data indicate that this fluorinated organosiloxane is suitable as the matrix resin for the fabrication of devices used in 5G communication.

Reversible Redox Crosslinking of Thiopropylsilicones.

Most silicone elastomers are thermosets. As a response to the new paradigm of polymer recyclability, the development of silicone elastomers that can be reversibly and repeatedly cured and uncrosslinked using redox conditions is reported. Thiopropyl-modified silicones are oxidized to elastomers with disulfide crosslinks using the organosoluble oxidant PhI(OAc)2 . As with any elastomer, mechanical properties can be tuned by varying crosslink density. Thermal stabilities in air show that the products are comparable to traditional silicone thermosets, with degradation only starting over 300°C. Uncrosslinking back to the same thiopropyl-modified silicones involves reductive S-S bridge cleavage using a Piers-Rubinsztajn reaction with hydrosilanes catalyzed by B(C6 F5 )3 ; HSiMe2 OSiMe3 is identified as a convenient reducing agent. The initially formed silicone-(CH2 )3 S-SiMe2 OSiMe3 products need deprotection with water in isopropanol/water to completely regenerate the thiopropylsilicones. This oxidation/reduction crosslinking/uncrosslinking cycle is practiced thrice, with a yield of 89% per cycle, with essentially no change in the Young's moduli of the elastomers, or 1 H NMR spectra of the uncrosslinked fluids after reduction. Further oxidation of disulfide groups on the elastomer surface permanently and significantly improved water wettability.