Palladium-catalyzed Mizoroki-Heck reactions in water using thermoresponsive polymer micelles

Suzuki, Noriyuki; Takabe, Taiga; Yamauchi, Yoshiko; Koyama, Shun; Koike, Rina; Rikukawa, Masahiro; Liao, Wei‐Ting; Peng, Wen-Sheng; Tsai, Fu‐Yu

doi:10.1016/j.tet.2019.01.047

Cited by 21 publications

(26 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Triethylammonium hypophosphite was prepared from triethylamine and hypophosphinic acid in toluene. The diblock copolymer NS was prepared as previously reported [ 45 , 55 , 56 , 57 , 58 , 59 , 60 , 61 ]. Dialysis was performed using Spectra/Por ® RC tubing (MWCO: 3.5kD).…”

Section: Methodsmentioning

confidence: 99%

“…For organic synthetic methods, there have also been many reports in which PNIPAAm was applied for organic reactions, as well as transition metal-catalyzed reactions. Many of these studies involve the use of a cross-linked PNIPAAm gel [ 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 ]; however, examples of thermoresponsive micelles applied for organic synthesis are still rare [ 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 ]. We previously reported the utilization of PNIPAAm block copolymers that form thermoresponsive micelles in water for organic synthesis.…”

Section: Introductionmentioning

confidence: 99%

“…O’Reilly and coworkers also reported the use of PNIPAAm-based copolymer micelles bearing L-proline for asymmetric reactions in water [ 48 ]. We recently reported palladium-catalyzed Mizoroki–Heck reactions in water using these thermoresponsive polymer micelles [ 45 ] and showed that these reactions gave the products in high yields and with a good extraction efficiency. In the previous study, we reported that more efficient extraction was observed for aqueous solutions of the diblock copolymer poly( N -isopropylacrylamide)- b -poly(sodium 4-styrenesulfonate) (PNIPAAm- b -PSSNa, NS ) compared to PNIPAAm -b -PEG, although the E-factor was still no less than 20.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Palladium-Catalyzed Mizoroki–Heck and Copper-Free Sonogashira Coupling Reactions in Water Using Thermoresponsive Polymer Micelles

et al. 2021

Self Cite

View full text Add to dashboard Cite

A few kinds of thermoresponsive diblock copolymers have been synthesized and utilized for palladium-catalyzed coupling reactions in water. Poly(N-isopropylacrylamide) (PNIPAAm) and poly(N,N-diethylacrylamide) (PDEAAm) are employed for thermoresponsive segments and poly(sodium 4-styrenesulfonate) (PSSNa) and poly(sodium 2-acrylamido-methylpropanesulfonate) (PAMPSNa) are employed for hydrophilic segments. Palladium-catalyzed Mizoroki–Heck reactions are performed in water and the efficiency of the extraction process is studied. More efficient extraction was observed for the PDEAAm copolymers when compared with the PNIPAAm copolymers and conventional surfactants. In the study of the Sonogashira coupling reactions in water, aggregative precipitation of the products was observed. Washing the precipitate with water gave the product with satisfactory purity with a good yield.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Palladium-Catalyzed Mizoroki–Heck and Copper-Free Sonogashira Coupling Reactions in Water Using Thermoresponsive Polymer Micelles

et al. 2021

Self Cite

View full text Add to dashboard Cite

show abstract

“…The 1,1-diphenylethylene side product likewise increased for the ortho -substituted ligand. The PdCl 2 (PPh 3 )-catalyzed Heck coupling of iodobenzene and various alkenes in water was also realized with thermoresponsive micelles with either non-ionic corona (PEO- b -PNIPAAm prepared by ATRP) and anionic corona (PSSNa- b -PNIPAAm prepared by RAFT) [ 104 ]. The BCP micelles were not modified with ligands, but the PdCl 2 (PPh 3 ) catalyst and substrates migrated into the hydrophobic core when the solution was heated above the LCST of PNIPAAm.…”

Section: Block Copolymer Micellesmentioning

confidence: 99%

Recent Advances in the Synthesis and Application of Polymer Compartments for Catalysis

et al. 2020

View full text Add to dashboard Cite

Catalysis is one of the most important processes in nature, science, and technology, that enables the energy efficient synthesis of essential organic compounds, pharmaceutically active substances, and molecular energy sources. In nature, catalytic reactions typically occur in aqueous environments involving multiple catalytic sites. To prevent the deactivation of catalysts in water or avoid unwanted cross-reactions, catalysts are often site-isolated in nanopockets or separately stored in compartments. These concepts have inspired the design of a range of synthetic nanoreactors that allow otherwise unfeasible catalytic reactions in aqueous environments. Since the field of nanoreactors is evolving rapidly, we here summarize—from a personal perspective—prominent and recent examples for polymer nanoreactors with emphasis on their synthesis and their ability to catalyze reactions in dispersion. Examples comprise the incorporation of catalytic sites into hydrophobic nanodomains of single chain polymer nanoparticles, molecular polymer nanoparticles, and block copolymer micelles and vesicles. We focus on catalytic reactions mediated by transition metal and organocatalysts, and the separate storage of multiple catalysts for one-pot cascade reactions. Efforts devoted to the field of nanoreactors are relevant for catalytic chemistry and nanotechnology, as well as the synthesis of pharmaceutical and natural compounds. Optimized nanoreactors will aid in the development of more potent catalytic systems for green and fast reaction sequences contributing to sustainable chemistry by reducing waste of solvents, reagents, and energy.

show abstract

“…The PNIPAM is hydrophilic and soluble in water under LCST, but becomes hydrophobic and insoluble in water above LCST. Several studies have utilized PNIPAM or its copolymers to design a variety of smart catalytic systems, such as thermo‐responsive hydrogel, 11 micelle, 12 microgel, 13 nanotube, 14 and polymer@metal nanoparticles 15 . Among the various thermo‐responsive catalytic systems based on polymers, the amphiphilic block copolymers are particularly attractive because of their unique solution properties, they can form polymer micelles in appropriate solvents system.…”

Section: Introductionmentioning

confidence: 99%

Thermo‐responsive block copolymer micelle‐supported (S)‐α,α‐diphenylprolinol trimethylsilyl ether for asymmetric Michael addition of nitroalkenes and aldehydes in water

Wang

et al. 2020

J of Applied Polymer Sci

View full text Add to dashboard Cite

An amphiphilic block copolymer PNIPAM53‐b‐(PS30‐co‐P4AMS10) was facilely prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization. The immobilization of (S)‐α,α‐diphenylprolinol trimethylsilyl ether onto the block copolymers was then performed through using copper‐catalyzed alkyne‐azide cycloaddition (CuAAC), and the generating amphiphilic diblock copolymer supported chiral catalyst PNIPAM53‐b‐(PS30‐co‐P4AMS10)/proTMS was self‐assembled into micelles with regular diameters about 50 nm in aqueous solution. The micellar catalyst was further used for the asymmetric Michael reaction between propanal and trans‐β‐nitrostyrene in water. Using only 1 mol% micellar catalyst, the corresponding Michael addition products could be obtained in good yields and high enantioselectivities as well as good diastereoselectivities. In addition, this micellar catalyst could be reused at least for four times. Moreover, the micellar catalyst could be applied for the asymmetric addition reaction of 4‐chlorocinnamyl aldehyde and nitromethane, and thus constructing the baclofen pharmaceutical intermediate.

show abstract

Palladium-catalyzed Mizoroki-Heck reactions in water using thermoresponsive polymer micelles

Cited by 21 publications

References 34 publications

Palladium-Catalyzed Mizoroki–Heck and Copper-Free Sonogashira Coupling Reactions in Water Using Thermoresponsive Polymer Micelles

Palladium-Catalyzed Mizoroki–Heck and Copper-Free Sonogashira Coupling Reactions in Water Using Thermoresponsive Polymer Micelles

Recent Advances in the Synthesis and Application of Polymer Compartments for Catalysis

Thermo‐responsive block copolymer micelle‐supported (S)‐α,α‐diphenylprolinol trimethylsilyl ether for asymmetric Michael addition of nitroalkenes and aldehydes in water

Contact Info

Product

Resources

About