How good is CuAAC “click” chemistry for polymer coupling reactions?

¹H NMR and SEC analyses are used to investigate the overall efficiency of Copper Catalyzed Azide Alkyne Cycloaddition (CuAAC) “click” coupling reactions between alkyne‐ and azide‐terminated polymers using polystyrene as a model. Quantitative convolution modeling of the entire molecular weight distribution is applied to characterize the outcomes of the functional polymer synthesis reactions (i.e., by atom transfer radical polymerization), as well as the CuAAC coupling reaction. Incomplete functionality of the azide‐terminated polystyrene (∼92%) proves to be the largest factor compromising the efficacy of the CuAAC coupling reaction and is attributed primarily to the loss of terminal bromide functionality during its synthesis. The efficiency of the S_N2 reaction converting bromide to azide was found to be about 99%. After taking into account the influence of non‐functional polymer, we find that, under the reaction conditions used, the efficiency of the CuAAC coupling reaction determined from both techniques is about 94%. These inefficiencies compromise the fidelity and potential utility of CuAAC coupling reactions for the synthesis of hierarchically structured polymers. While CuAAC efficiency is expected to depend on the specific reaction conditions used, the framework described for determining reaction efficiency does provide a means for ultimately optimizing the reaction conditions for CuAAC coupling reactions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 75–84     

Amine Salt–Catalyzed Synthesis of 5-Substituted 1H-Tetrazoles from Nitriles

The [3 + 2] cycloaddition reaction between sodium azide and various organic nitriles proceeds smoothly in the presence of amine salts as catalyst in dimethylformamide. The corresponding 5-substituted 1-H tetrazoles were obtained under mild condition in good to excellent yields. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

Synthesis of (22R, 25R)-3β,26-Dihydroxy-5α-furostan-6-one #

The synthesis of a plant growth promoter furostanol which bears the characteristic functionality of teasterone on rings A and B is described.

     

Co (II)‐C12 alkyl carbon chain multi‐functional ionic liquid immobilized on nano‐SiO2 nano‐SiO2@CoCl3‐C12IL as an efficient cooperative catalyst for C–H activation by direct acylation of aryl halides with aldehydes

Nano‐silica supported ionic liquids composed of alkyl carbon chain and transition metal chlorides anions have been prepared and successfully applied as a heterogeneous catalyst in the direct aldehyde C‐H activation. Catalytic results indicated that nano‐SiO₂ supported ionic liquid consisting C12 alkyl carbon chain and CoCl₃ anion nano‐SiO₂@CoCl₃‐C12IL showed excellent catalytic properties with good to excellent yields towards the desired aryl ketones. The excellent recyclability of the supported catalyst, mild reaction conditions, low catalyst loading, and operational simplicity are the important features of this methodology.     

Copper(I) oxide nanoparticles supported on magnetic casein as a bio‐supported and magnetically recoverable catalyst for aqueous click chemistry synthesis of 1,4‐disubstituted 1,2,3‐triazoles

Copper(I) oxide nanoparticles supported on magnetic casein (Cu₂O/Casein@Fe₃O₄NPs) has been synthesized as a bio‐supported catalyst and was characterized using powder X‐ray diffraction, transmission electron microscopy, energy dispersive X‐ray and Fourier transform infrared spectroscopies, thermogravimetric analysis and inductively coupled plasma optical emission spectrometry. The catalytic activity of the synthesized catalyst was investigated in one‐pot three‐component reactions of alkyl halides, sodium azide and alkynes to prepare 1,4‐disubstituted 1,2,3‐triazoles with high yields in water. The reaction work‐up is simple and the catalyst can be magnetically separated from the reaction medium and reused in subsequent reactions.     

Synthesis of diaryl sulfides via nickel ferrite‐catalysed C─S bond formation in green media

NiFe₂O₄ magnetic nanoparticles (MNPs) were synthesized, characterized and applied as an air‐stable, inexpensive and magnetically separable nanocatalyst for the synthesis of structurally diverse sulfides. Efficient methodologies were developed for the synthesis of unsymmetric diaryl sulfides via odourless and one‐pot reactions of triphenyltin chloride/S₈ or arylboronic acid/S₈ as thiolating agents with aryl halides or nitroarenes as starting materials in the presence of base (K₂CO₃ or NaOH) and NiFe₂O₄ MNPs as a catalyst in water or poly (ethylene glycol) as solvent at 80–110 °C. Free from ligand and the unpleasant smell of thiols and with the use of magnetically reusable nanocatalyst, green solvents and commercially available and cheap sulfur source and starting materials, these methods are more eco‐friendly and practical than available protocols for the synthesis of sulfides.     

Poly(aryl ether ketone) composite membrane as a high‐performance lithium‐ion batteries separator

We described the design and synthesis of a modified poly(aryl ether ketone) bearing phenolphthalein and allyl groups (P‐PAEK) via nucleophilic polycondensation. A new kind of composite separator, crosslinked P‐PAEK/polyvinylidene fluoride (c‐P‐PAEK/PVDF) membrane was successfully prepared using phase separation, phase inversion method, and UV crosslinking technique. As a separator of lithium‐ion battery, c‐P‐PAEK/PVDF membrane demonstrates high porosity and uniform distribution of pores with interconnected pathways. Low thermal shrinkage, distinct shut‐down effect, high liquid electrolyte uptake capacity, and exciting liquid electrolyte wettability of the prepared c‐P‐PAEK/PVDF membrane have been revealed through comprehensive study. Moreover, the c‐P‐PAEK/PVDF membrane was applied to assemble a conventional Li/LiFePO₄ coin cell, which exhibited hopeful cell performance. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2714–2721     

Synergistic Activities in the Ullmann Coupling of Chloroarenes at Ambient Temperature by Pd‐Supported Calcined Ferrocenated La2O3

Novel palladium‐doped nanoparticles have been explored to serve as the first metal oxide‐derived heterogeneous catalyst for Ullmann reaction of chloroarenes under mild condition (34 °C). This heterogeneous catalyst exhibited high catalytic activity towards the Ullmann homocoupling of chloroarenes into a series of useful symmetrically biaryl products with good to excellent yields in the presence of ethanol and NaOH, thereby leading to green and economical Ullmann reaction. The produced nanoparticles were successfully characterized by various techniques including PXRD, XPS, HRTEM, SEM‐EDS, BET, TGA techniques, elemental mapping analysis and ICP‐OES. Interestingly, based on characterization and experimental data, a reasonable mechanism has been proposed. Also, the formation of aryl methyl ketone as a by‐product has been further confirmed by isotopic labelling experiments that the acetyl moiety is derived from ethanol. Moreover, the catalyst was stable and could be easily reused up to 5 times under atmospheric air without suffering significant loss in catalytic activity.