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Herein, we demonstrated an effective protocol for the regioselective ring opening of epoxides with alcohols. By following this strategy, both α‐alkylated ketones and β‐alkylated secondary alcohols were selectively obtained by changing the reaction parameters. Compared to the previously reported protocols, this methodology was operated using considerably lower base at lower temperature. Notably, a wide array of substrates with tolerance of different functional groups was demonstrated. A series of control experiments and deuterium‐labelling experiments were performed to understand this catalytic process. [ABSTRACT FROM AUTHOR]

A series of functional cross-linked polystyrenes was synthesized by the free radical copolymerization of divinylbenzene with functional styrenes and utilized as heterogeneous catalysts for the coupling of epoxides with CO2. Investigations showed that the cross-linked copolymer functionalized by quaternary ammonium chloride (CP1) exhibited high catalytic activity in the coupling reaction and thermostability at elevated temperatures. Thus, CP1 was easily recycled from the reaction mixture by filtration and reused without obvious loss of activity. Moreover, the activity of CP1 can be greatly enhanced by adding conventional Lewis acids such as anhydrous FeCl3 or AlCl3. Thus, copolymer 1/FeCl3 composites (1/1 molar ratio) transformed propylene oxide and CO2 to propylene carbonate in 92% yield in 10 h at 110 °C with the composite catalyst loading of 0.25 mol% with respect to propylene oxide and can be reused after simple filtration without significant decline of activity. [ABSTRACT FROM AUTHOR]

Catalytic hydrogenation of carbon dioxide (CO2) for the preparation of higher carboxylic acids is attractive and promising. Herein, we demonstrate a general strategy for producing higher carboxylic acids via reaction of CO2 and H2 with light (C2~C4) oxygenates such as ketones, alcohols, polyols, ethers and epoxides. In a green solvent consisting of ionic liquid (1‐ethyl‐3‐methylimidazolium iodide) and water, the reaction can be efficiently accelerated by RhI3 catalyst and I2 promoter at 170 °C. Very high or remarkable yields of higher carboxylic acids were synthesized via C−C bond formation between the intermediates generated from the oxygenates and CO2. Detailed study indicated that the catalyst and the solvent had excellent synergistic effect for promoting the reaction. The strategy can effectively convert the bulk and inexpensive feedstocks to value‐added carboxylic acids, and therefore is promising for commercial application. [ABSTRACT FROM AUTHOR]

Catalytic hydrogenation of carbon dioxide (CO2) for the preparation of higher carboxylic acids is attractive and promising. Herein, we demonstrate a general strategy for producing higher carboxylic acids via reaction of CO2 and H2 with light (C2~C4) oxygenates such as ketones, alcohols, polyols, ethers and epoxides. In a green solvent consisting of ionic liquid (1‐ethyl‐3‐methylimidazolium iodide) and water, the reaction can be efficiently accelerated by RhI3 catalyst and I2 promoter at 170 °C. Very high or remarkable yields of higher carboxylic acids were synthesized via C−C bond formation between the intermediates generated from the oxygenates and CO2. Detailed study indicated that the catalyst and the solvent had excellent synergistic effect for promoting the reaction. The strategy can effectively convert the bulk and inexpensive feedstocks to value‐added carboxylic acids, and therefore is promising for commercial application. [ABSTRACT FROM AUTHOR]

Chemoselective hydrogenation of α,β‐epoxy ketones and α‐ketoamides is achieved at room temperature (25 °C) using 2.0 bar H2 and a pincer‐ligated Mn(I) catalyst that provides synthetically valuable α‐hydroxy epoxides and α‐hydroxy amides. This protocol applies to a wide range of alkyl‐ and aryl‐substituted α,β‐epoxy ketones, including terpenes (α‐ionone, nootkatone, and R‐carvone)‐ and steroids (testosterone and progesterone)‐derived epoxy ketones, and tolerates H2 sensitive functionalities, such as halides, acetyl, nitrile, nitro, epoxide, alkenyl and alkynyl groups. Additionally, α‐ketoamides bearing reducible functional groups, including acetyl and diazo benzene, were untouched under this protocol and selectively converted to α‐hydroxy amides. A preliminary mechanistic study highlighted the metal‐ligand cooperative H2 activation process. [ABSTRACT FROM AUTHOR]

A novel CCOF core–shell composite material (S)-DTP-COF@SiO2 was prepared via asymmetric catalytic and in situ growth strategy. The prepared (S)-DTP-COF@SiO2 was utilized as separation medium for HPLC enantioseparation using normal-phase and reversed-phase chromatographic modes, which displays excellent chiral separation performance for alcohols, esters, ketones, and epoxides, etc. Compared with chiral commercial chromatographic columns (Chiralpak AD-H and Chiralcel OD-H columns) and some previously reported chiral CCOF@SiO2 (CC-MP CCTF@SiO2 and MDI-β-CD-modified COF@SiO2)-packed columns, there are 4, 3, 13, and 15 tested racemic compounds that could not be resolved on the Chiralpak AD-H column, Chiralcel OD-H column, CC-MP CCTF@SiO2 column, and MDI-β-CD-modified COF@SiO2 column, respectively, which indicates that the resolution effect of (S)-DTP-COF@SiO2-packed column can be complementary to the other ones. The effects of the analyte mass, column temperature, and mobile phase composition on the enantiomeric separation were investigated. The chiral column exhibits good reproducibility after multiple consecutive injections. The RSDs (n = 5) of the peak area and retention time were less than 1.5% for repetitive separation of 2-methoxy-2-phenylethanol and 1-phenyl-1-pentanol. The chiral core–shell composite (S)-DTP-COF@SiO2 exhibited good enantiomeric separation performance, which not only demonstrates its potential as a novel CSP material in HPLC but also expands the range of applications for chiral COFs. [ABSTRACT FROM AUTHOR]

Microelectronics packages play a vital role in not only interconnecting the electronic signals from the die to the printed circuit board (PCB), but also in protecting the chips during the manufacturing process and their subsequent service lives. Epoxy molding compound (EMC) is widely used in electronic packaging due to its superior processing capability and low circuit signal delay. However, interfacial delamination is a common problem in encapsulated silicon devices, particularly at the interface between the copper leadframe (LF) pads and the EMC due to the weaker adhesion strength. Accordingly, the present study employs a double cantilever beam (DCB) experimental testing method and a numerical model based on the virtual crack closure technique (VCCT) to investigate the fracture behavior at the EMC/Cu LF interface in a quad flat no leads (QFN) package. The experiments are performed on an MTS-Acumen microforce tester equipped with a load unit capable of applying a force of 0.01 to 1250 N with a displacement resolution of 0.1 μm. The DCB specimens are prepared with a pre-crack length of 12 mm. The validity of the simulation model is confirmed by comparing the predicted values of the critical strain energy release rate (SERR, Gc) between the EMC and the copper LF pads with the experimental observations. In general, the results show that the Gc value provides a useful parameter for evaluating the delamination risk of encapsulated microelectronics packages and assessing the reliability of alternative package architectures. [ABSTRACT FROM AUTHOR]

Background: Ethylene oxide, a reactive epoxy compound, has been widely used in various industries for many years. However, evidence of the combined toxic effects of ethylene oxide exposure on the liver is still lacking. Methods: We analyzed the merged data from the National Health and Nutrition Examination Survey (NHANES) from 2013 to 2016. Ultimately, 4141 adults aged 18 and over were selected as the sample. We used linear regression to explore the association between blood ethylene oxide and LFT indicators. Results: The weighted linear regression model showed that HbEO is positively correlated with ALP (β = 2.61, 95% CI 1.97, 3.24, p < 0.0001), GGT (β = 5.75, 95% CI 4.46, 7/05, p < 0.0001), ALT (β = 0.50, 95% CI 0.09, 0.90, p = 0.0158), and AST (β = 0.71, 95% CI 0.44, 0.98, p < 0.0001) and negatively correlated with TBIL (β = −0.30, 95% CI −0.43, −0.16, p < 0.0001). Conclusions: Ethylene oxide exposure is significantly associated with changes in liver function indicators among adults in the United States. Future work should further examine these relationships. [ABSTRACT FROM AUTHOR]

Chiral epichlorohydrin (ECH) is an attractive intermediate for chiral pharmaceuticals and chemicals preparation. The asymmetric synthesis of chiral ECH using 1,3-dicholoro-2-propanol (1,3-DCP) catalyzed by a haloalcohol dehalogenase (HHDH) was considered as a feasible approach. However, the reverse ring opening reaction caused low optical purity of chiral ECH, thus severely restricts the industrial application of HHDHs. In the present study, a novel selective conformation adjustment strategy was developed with an engineered HheCPS to regulate the kinetic parameters of the forward and reverse reactions, based on site saturation mutation and molecular simulation analysis. The HheCPS mutant E85P was constructed with a markable change in the conformation of (S)-ECH in the substrate pocket and a slight impact on the interaction between 1,3-DCP and the enzyme, which resulted in the kinetic deceleration of the reverse reactions. Compared with HheCPS, the catalytic efficiency (kcat(S)-ECH/Km(S)-ECH) of the reversed reaction dropped to 0.23-fold (from 0.13 to 0.03 mM−1 s−1), while the catalytic efficiency (kcat(1,3-DCP)/Km(1,3-DCP)) of the forward reaction only reduced from 0.83 to 0.71 mM−1 s−1. With 40 mM 1,3-DCP as substrate, HheCPS E85P catalyzed the synthesis of (S)-ECH with the yield up to 55.35% and the e.e. increased from 92.54 to >99%. Our work provided an effective approach for understanding the stereoselective catalytic mechanism as well as the green manufacturing of chiral epoxides. [ABSTRACT FROM AUTHOR]

The spliceosome is a staggeringly complex machine, comprising, in humans, 5 snRNAs and >150 proteins. We scaled haploid CRISPR-Cas9 base editing to target the entire human spliceosome and investigated the mutants using the U2 snRNP/SF3b inhibitor, pladienolide B. Hypersensitive substitutions define functional sites in the U1/U2-containing A complex but also in components that act as late as the second chemical step after SF3b is dissociated. Viable resistance substitutions map not only to the pladienolide B-binding site but also to the G-patch domain of SUGP1, which lacks orthologs in yeast. We used these mutants and biochemical approaches to identify the spliceosomal disassemblase DHX15/hPrp43 as the ATPase ligand for SUGP1. These and other data support a model in which SUGP1 promotes splicing fidelity by triggering early spliceosome disassembly in response to kinetic blocks. Our approach provides a template for the analysis of essential cellular machines in humans.

Reported herein is a stereoselective route to anti -β-hydroxy sulfoxides through the reaction of epoxides with sulfenate anions. Extensive experimental/computational studies revealed the dual special roles of MgBr2 ·OEt2 , serving to generate the bromohydrin alkoxide intermediate, which undergoes nucleophilic attack on the prochiral sulfenate in a diastereoselective manner. The present study has opened a general stereoselective synthetic route to anti -β-hydroxy sulfoxides. [ABSTRACT FROM AUTHOR]

Using carbon disulfide (CS2) and carbonyl sulfide (COS) as sulfur‐containing and one‐carbon feedstocks to make value‐added products is paramount for both pure and applied chemistry and environmental science. One of the practical strategies is to copolymerize these bulk chemicals with epoxides to produce sulfur‐containing polymers. This approach contributes to improving the sustainability of polymer manufacturing, provides highly desired functional polymer materials, and has attracted much attention. However, these copolymerizations invariably exhibit the intensely complicated chemistry of O/S exchange reaction, leading to sulfur‐containing polymers with diverse architectures. As the understanding of O/S exchange continues to deepen, recent efforts have guided significant advances in the synthesis of CS2‐ and COS‐based polymers. This review examines the O/S exchange chemistry and summarizes the recent progress in this field to promote the further advance of synthesizing sulfur‐containing polymers from CS2 and COS. [ABSTRACT FROM AUTHOR]

Borane catalysis has emerged as a powerful technology in epoxide polymerization. Still, the structure‐activity correlations for these catalysts are not fully understood to date, especially regarding compounds with nonionic backbones. Thus, in this work, 13 different borane catalysts of this respective type are described and investigated for their epoxide oligomerization and polymerization performance, using propylene oxide (PO), 1‐butylene oxide (BO) and allyl glycidyl ether (AGE) as monomers. Structurally, special emphasis is put on catalysts with different linker lengths and linker flexibilities as well as the introduction of more than two borane functionalities. Importantly, this screening is conducted both under typical polymerization conditions as well as under the chain transfer agent (CTA)‐rich conditions relevant for large‐scale production. It is found that suitable preorganization of the borane groups, such as present in biphenyl derivatives, offers a simple route to high‐performing catalysts and quantitative monomer conversion of the investigated epoxides. Furthermore, it is demonstrated that a diborane‐catalyzed oligomerization can be kept active over weeks, whereby repeated addition of monomer batches (14 steps) constantly results in full conversion and well‐defined oligoethers, underlining the practical potential of this method. The absence of co‐initiating counter ions is suggested as an inherent advantage of nonionic catalysts. [ABSTRACT FROM AUTHOR]

The alkylation of arenes is one of the most fundamental transformations in synthetic chemistry and the transition‐metal‐catalyzed direct C−H alkylation represents a straightforward and attractive approach from both atom and step‐economy perspectives. Epoxides, the smallest three‐membered saturated O‐heterocycles that can be easily prepared in racemic or enantioenriched forms, are highly useful building blocks for the synthesis of complex organic molecules. Owing to their inherent high ring‐strain, epoxides readily undergo ring‐opening reactions and have been used as alkylating reagents for C−H alkylation catalyzed by transition metals. This review summarizes recent advances in utilizing epoxides as alkylating reagents in transition‐metal‐catalyzed C−H alkylation as well as their synthetic applications in organic synthesis. [ABSTRACT FROM AUTHOR]

Transition metal‐catalyzed epoxidation of carbonyl compounds through carbonyl ylides represents a highly effective method for synthesizing a diverse range of valuable epoxides. This review offers an in‐depth overview of the latest developments in inter‐ and intramolecular epoxidation reactions involving metal carbenes and carbonyl compounds, encompassing both racemic to enantioselective transformations. These catalytic epoxidations are reviewed by highlighting their product selectivity, diversity and applicability, and the related mechanistic rationale is showcased where possible. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Eight zwitterionic rare earth metal complexes stabilized by amino‐bridged tris(phenolato) ligands bearing quaternary ammonium side‐arms were synthesized and characterized. These complexes were used as single‐component catalysts for the cycloaddition of CO2 and epoxides, and their catalytic activities are obviously higher than those of their binary analogues. Further studies revealed that the halide anions (Cl–, Br–, I–) and the metal complexes influenced the catalytic activity, and the lanthanum complex bearing iodide anion showed the highest catalytic activity for this addition reaction. A variety of mono‐substituted epoxides were converted to cyclic carbonates in good to excellent yields (55%—99%) with high selectivity (> 99%) at 30 °C and 1 bar CO2, whereas internal epoxides required higher both reaction temperatures (60—120 °C) and catalyst loading (2 mol%) for high yields. The catalyst was recyclable for four times without noticeable loss of catalytic activity. Based on the results of kinetic studies and in situ IR reactions, a plausible reaction mechanism was proposed. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The utilization of carbon dioxide (CO2) as a C1 feedstock is consistently attractive, especially in the preparation of sustainable polymeric materials. In this contribution, a terpolymer of CO2, 1,3‐butadiene (BD) and epoxide is synthesized by scandium triflate catalyzed cationic ring‐opening copolymerization of α‐ethylidene‐δ‐vinyl‐δ‐valerolactone (EVL), an intermediate derived from CO2 and BD, with epoxides. The obtained terpolymer with a CO2 content of 22 mol% has a number‐average molecular weight (Mn) up to 7.8 kg/mol and a dispersity (Đ) of 2.4. The reactivity ratios of EVL and cyclohexene oxide (CHO) are determined as 0.01 and 1.07, respectively, suggesting random characteristic of the terpolymer. The preserved C=C double bonds from BD allow for the further modification of the terpolymer by photoinitiated crosslinking. The yielded networks are fluorescent and degradable. This method offers enhanced versatility to the synthesis and additional functionalization of CO2‐based polymers. [ABSTRACT FROM AUTHOR]

We describe a highly stereoconvergent radical epoxide allylation towards diastereomerically and enantiomerically enriched α‐quaternary alcohols in two steps from olefins. Our approach combines the stereospecifity and enantioselectivity of the Shi epoxidation with the unprecedented Ti(III)‐promoted intramolecular radical group transfer allylation of epoxides. A directional isomerization step via configurationally labile radical intermediates enables the selective preparation of all‐carbon quaternary stereocenters in a unique fashion. [ABSTRACT FROM AUTHOR]

In this study, the impact of ethylene oxide, propylene oxide, 1,2-butene oxide, and 1,2-pentene oxide on the polymerization of propylene at an industrial level was investigated, focusing on their influence on the catalytic efficiency and the properties of polypropylene (PP) without additives. The results show that concentrations between 0 and 1.24 ppm of these epoxides negatively affect the reaction's productivity, the PP's mechanical properties, the polymer's fluidity index, and the PP's thermal properties. Fourier transform infrared spectroscopy (FTIR) revealed bands for the Ti-O bond and the Cl-Ti-O-CH2 bonds at 430 to 475 cm−1 and 957 to 1037 cm−1, respectively, indicating the interaction between the epoxides and the Ziegler–Natta catalyst. The thermal degradation of PP in the presence of these epoxides showed a similar trend, varying in magnitude depending on the concentration of the inhibitor. Sample M7, with 0.021 ppm propylene oxide, exhibited significant mass loss at both 540 °C and 600 °C, suggesting that even small concentrations of this epoxide can markedly increase the thermal degradation of PP. This pattern is repeated in samples with 1,2-butene oxide and 1,2-pentene oxide. These results highlight the need to strictly control the presence of impurities in PP production to optimize both the final product's quality and the polymerization process's efficiency. [ABSTRACT FROM AUTHOR]

Currently, the flame retardancy of epoxy resin (EP) was achieved at the expenses of the transparency and/or toughness. In the present work, a phosphorus/nitrogen‐containing compound (FDNP) was synthesized by one‐pot method using 9,10‐dihydro‐9‐oxa‐10‐phospha‐phenanthrene‐10‐oxide, furfural and N‐phenyl‐p‐phenylenediamine as raw materials, and further adopted as a functional agent for epoxy resin. The results demonstrated that the FDNP remarkably improved the fire safety of EP. The incorporation of 4 wt% FDNP enabled EP to pass UL‐94 V‐0 rating test and achieve a limiting oxygen index value of 35.5%; meanwhile, the peak heat release rate, total heat release rate and total smoke release were significantly reduced by 41.3%, 41.6% and 72.5% as compared with the pure EP, respectively. What is more, the EP/4 wt% FDNP composite kept almost the same transparency of the pure EP, simultaneously its impact strength was more than doubled as that of the pure EP. Herein, the improved flame retardancy is contributed to a synergistic biphasic flame retardant effect including the formation of a compact protective carbon layer and the release of both non‐combustible gases and phosphorus‐containing radicals. [ABSTRACT FROM AUTHOR]

Background: Zinc fever is well described in medical literature, particularly in workers after handling zinc-containing materials at high temperatures e.g., in the welding of hot-dip galvanized steel sheets. It is not known whether zinc fever also occurs at low temperatures. Case presentation: We present the case of a 33-year-old Caucasian atopic painter and varnisher with work-related dyspnea, sweating, as well as multiple occurrences of fever. He was sent to Institute for Prevention and Occupational medicine of the German Social Accident Insurance, Institute of the Ruhr-Universität Bochum (IPA) for the evaluation of isocyanate asthma, but an inhalative challenge with hexamethylene diisocyanate was negative. Since symptoms were closely related to the use of zinc coatings at room temperature without adequate protective measures, the diagnosis of zinc fever was made. After exposure cessation the worker immediately became symptom-free. The work as painter and varnisher may be associated with various exposures to hazardous substances. Besides solvents, epoxy compounds and isocyanates, which can cause obstructive respiratory diseases; additionally, zinc-containing agents should be considered as health hazards. Conclusions: This case demonstrates that zinc fever may occur also after application of zinc coatings by spray painting at low temperatures. [ABSTRACT FROM AUTHOR]

Multimetallic synergistic effects have the potential to improve CO2 cycloesterification and Knoevenagel reaction processes, outperforming monometallic MOFs. The results demonstrate superior performance in these processes. To investigate this, we created and characterized a selection of single‐component Ln(III)‐MOFs (Ln=Eu, Tb, Gd, Dy, Ho) and high‐entropy lanthanide‐organic framework (HE‐LnMOF) using solvent‐thermal conditions. The experiments revealed that HE‐LnMOF exhibited heightened catalytic efficiency in CO2 cycloesterification and Knoevenagel reactions compared to single‐component Ln(III) MOFs. Moreover, the HE‐LnMOF displayed significant stability, maintaining their structural integrity after five cycles while sustaining elevated conversion and selectivity rates. The feasible mechanisms of catalytic reactions were also discussed. HE‐LnMOF possess multiple unsaturated metal centers, acting as Lewis acid sites, with oxygen atoms connecting the metal, and hydroxyl groups on the ligand serving as base sites. This study introduces a novel method for synthesizing HE‐LnMOF and presents a fresh application of HE‐LnMOF for converting CO2. [ABSTRACT FROM AUTHOR]

The ternary copolymerization of a series of cyclic anhydrides with epoxides and carbon dioxide using dinuclear [OSSO]‐type chromium (III),1, and ‐iron(III), 2, complexes (0.1 mol %) in combination with (bis(triphenylphosphine)iminium chloride) (PPNCl, 0.5–1.0 mol with respect to catalyst) as co‐catalyst is reported in this study. The results have yielded copolymers with polyester and polycarbonate segments with high molecular weights and narrow dispersity. The catalytic systems 1–2/PPNCl were tested in the copolymerization of different epoxides, such as propylene oxide (PO), cyclohexene oxide (CHO), and vinylcyclohexene oxide (VCHO), with a variety of cyclic anhydrides, such as phthalic (PA), diglycolic (DGA) and succinic (SA), with CO2 pressure of 20 bar, temperature range of 45–80 °C in 24 h. Anhydride reaction, affording the polyester segments, exceeded the conversion of 99 % in all the explored cases. On the other hand, in the case of epoxide copolymerization with CO2, for the propylene oxide (PO) reaction, the selectivity towards polypropylene carbonate (PPC) without polyether linkage consistently was >99 %. For the terpolymerization of PO, CO2 and diglycolic anhydride (DGA), a notable epoxide conversion of 86 %, selectively to polycarbonate, with TOF value as high as 36 h−1, was achieved. [ABSTRACT FROM AUTHOR]

The cycloaddition of carbon dioxide to epoxide (CCE) reaction stands out as one of the few feasible chemical processes for catalytically fixing CO2. Traditionally, halide anions were frequently used as cocatalysts for catalysing the CCE reaction owing to their excellent nucleophilic and leaving abilities. However, halides are known for their corrosive effects on process reactors, and their treatment is challenging. Consequently, there is a substantial increase in the demand for halide-free catalysis in the CCE reaction. Herein, a series of bifunctional catalysts were designed for CCE reactions. The reactions were assessed under conditions of 120 °C and 1 MPa employing a catalyst loading of 0.5 mol% over 24 hours. The dual activation mechanism of the catalyst was confirmed through NMR titration and control experiments. As a bifunctional catalyst, the ion pair polarized the oxygen atom of epoxide via H-bonding with N+–H while the phenolate anion activated carbon dioxide simultaneously. This study introduces a pyridinium base binary organocatalyst as a halide-free hydrogen bond donor (HBD) anion organocatalyst with broad applicability for CO2 utilization. [ABSTRACT FROM AUTHOR]

To enrich 'epoxide hydrolase (EH) tool cabinet' for preparing enantiopure epoxides and 1,2-diols, a novel microbial EH, Sf EH2, was identified from Streptomyces fradiae SF-2. Bioinformatics analysis indicated that Sf EH2 has typical structural characteristics of α/β-hydrolase fold superfamily. Its coding gene, sfeh 2, was then codon-optimized and amplified. A recombinant (re) Sf EH2-expressing E. coli BL21(DE3) strain (E. coli / sfeh 2) was constructed through DNA manipulations. Substrate spectrum assay including fifteen common racemic (rac -) epoxides by E. coli / sfeh 2 showed that re Sf EH2 displayed the highest and best complementary regioselectivities (regioselectivity coefficients, α R = 89.7% and β S = 91.4%) towards rac - 14a , as well as the highest enantioselectivity (enantiomeric ratio, E = 15.3) in S -type towards rac - 15a. Molecular docking simulation revealed that Sf EH2 preferentially attacked C α of (R)- 14a and C β of (S)- 14a geometrically. In kinetic parameter analysis, the K m R (5.74 mM) of purified re Sf EH2 for (R)- 15a was 1.76-fold lower than K m S (10.09 mM) for (S)- 15a. At last, using 50 mg dry cell weight/mL E. coli / sfeh 2, the scale-up enantioconvergent hydrolysis of 100 mM rac - 14a at 30 °C for 6.0 h afforded (S)- 14b with 80.9% ee p and 90.1% yield, while the kinetic resolution of 150 mM rac - 15a retained (S)- 15a with >99.0% ee s and 42.2% yield. [Display omitted] • A novel epoxide hydrolase, Sf EH2, is identified and characterized. • Sf EH2 displays desired regioselectivity for racemic 4-methylphenyl glycidyl ether. • Sf EH2 displays desired enantioselectivity for racemic benzyl glycidyl ether phenyl. • Space-time yield of (S)-3-aryloxy-1,2-propanediol by Sf EH2 is the highest. • Space-time yield of (S)-benzyl glycidyl ether phenyl by Sf EH2 is the highest. [ABSTRACT FROM AUTHOR]

New oligoether diamines were synthesized via the step of obtaining oligoether diacrylates, followed by their subsequent reaction with 3-aminomethyl-3,5,5-trimethylcyclohexylamine. A series of urethane-containing elastomers based on them was obtained. The polymers were evaluated by differential scanning calorimetry, and their deformation and strength characteristics were also estimated. It was demonstrated that a low glass transition temperature is characteristic of all the polymers. [ABSTRACT FROM AUTHOR]

The development of transport technologies today requires not only the creation of bases for the optimal technical use of vehicles, their technical operation, but also their maintenance and repair. One of the main tasks of transport technologies is the search for new promising scientific directions and their implementation in practice, as well as ensuring the effective use of the latest technologies and innovative methods for the construction or repair of water transport facilities. In this respect, the use of epoxy-based polymer composites is promising. They are characterised by improved adhesive and cohesive properties compared to other known oligomers, which determines the wide range of their application in water transport. In order to improve the properties of epoxy-based adhesives, additives of different physical nature are introduced into the epoxy matrix at the initial stage of moulding. This paper investigates the effect of the modifier d-ascorbic acid on the thermal properties of epoxies to obtain a material intended for the restoration of ship loading mechanisms. Based on the dynamics of heat resistance as a function of d-ascorbic acid concentration, the optimum content of the additive in the epoxy compound was determined, which is 1,25...1,50 pts.wt.for 100 pts.wt.of epoxy resin. The introduction of a modifier into the epoxy oligomer provides composites with the highest heat resistance values of all the materials studied. The heat resistance values increase from 341 K (for the epoxy matrix) to 352...354 K. The mechanism of increasing the heat resistance of an epoxy matrix in the presence of a modifier is substantiated, which involves the interaction of epoxy resin with an additive and a hardener as a result of chemical reactions. As a result of the reactions of structure formation of the compound based on epoxy oligomer and modifier in the presence of polyethylene polyamine, mainly strong chemical bonds of C-O, NH2, O-NH2, N=O, N-O-H, C=N type are formed, which largely determine the increase of cohesive strength of the newly formed modified epoxy matrices. It should be noted that it is the cohesive strength of the matrix that determines the thermal resistance of the material at elevated temperatures. It was found that the maximum glass transition temperature (333 K) was observed for the modified material containing d-ascorbic acid at 1,5 pts.wt. At this level of additive, the maximum values of both heat resistance and glass transition temperature were observed compared to the original epoxy matrix (327 K). At this modifier concentration, the crosslinking of the compound forms the most cross-linked structural network of an amorphous polymer with the highest number of chemical bonds. [ABSTRACT FROM AUTHOR]

Polymer adhesion promoters were formulated to improve the adhesion strength of lead frame/epoxy composites. The poly(itaconic acid‐co‐acrylamide) (IAcAAM) was synthesized via free radical polymerization to improve the interfacial adhesion between Ni and Cu lead frames and epoxy composites. IAcAAM was synthesized by setting itaconic acid (IA) and acrylamide (AAM) at molar ratios of 7:3, 5:5, and 3:7. The interfacial adhesion mechanism was investigated by introducing IAcAAM with three different comonomer molar ratios. The adhesion strength between EMC and Cu and Ni substrates to which each IAcAAM was applied was measured using a universal testing machine, and the effect of IAcAAM with various IA:AAM molar ratios on the surface energy of EMC was closely studied. As a result, the adhesion properties of Ni lead frame/epoxy composite and Cu lead frame/epoxy composite were improved as small amounts of all IAcAAM samples were added to the epoxy mixture. We confirmed that IAcAAM with an appropriate molar ratio can be used in the EMC process and has the potential to increase the adhesion of epoxy composites and metal lead frames. Highlights: A polymeric adhesive promoter was synthesized to enhance the adhesion strength of lead frame/epoxy composites.Poly(itaconic acid‐co‐acrylamide) (IAcAAM) was copolymerized from itaconic acid and acrylamide for this purpose.The adhesion strength of lead frame/epoxy composites was compared for different IAcAAM monomer contents and with a commercial adhesive promoter.IAcAAM showed superior adhesion strength in the Ni lead frame/epoxy composite material.The highest adhesion strength was achieved at a monomer composition of 5:5. [ABSTRACT FROM AUTHOR]

Mesoionic N‐heterocyclic olefins (mNHOs) have recently emerged as a novel class of highly nucleophilic and super‐basic σ‐donor compounds. Making use of these properties in synthetic polymer chemistry, it is shown that a combination of a specific mNHO and a Mg‐based Lewis acid (magnesium bis(hexamethyldisilazide), Mg(HMDS)2) delivers poly(propylene oxide) in quantitative yields from the polymerization of the corresponding epoxide (0.1 mol% mNHO loading). The initiation mechanism involves monomer activation by the Lewis acid and direct ring‐opening of the monomer by nucleophilic attack of the mNHO, forming a zwitterionic propagating species. Modulation of the mNHO properties is thereby a direct tool to impact initiation efficiency, revealing a sterically unencumbered triazole‐derivative as particularly useful. The joint application of mNHOs together with borane‐type Lewis acids is also outlined, resulting in high conversions and fast polymerization kinetics. Importantly, while molar mass distributions remain relatively broad, indicating faster propagation than initiation, the overall molar masses are significantly lower than found in the case of regular NHOs, underlining the increased nucleophilicity and ensuing improved initiation efficiency of mNHOs. [ABSTRACT FROM AUTHOR]

A simple porous polymer framework (PPF) as a promising heterogeneous ligand for the Pd-catalyzed CO2 fixation reaction into diverse cyclic carbonates is reported. Several terminal epoxides and more challenging disubstituted epoxides were efficiently converted into value-added cyclic carbonates with satisfactory to excellent yields (i.e., 65 to 99% yields) and excellent selectivities (499%) using an imine-linked Pd-based PPF catalytic system (namely, Pd@3D PPF) as an efficient catalyst and tetrabutylammonium bromide (TBAB) as a co-catalyst under mild conditions (1 atm CO2 pressure and room-temperature) without employing any solvents. Notably, the Pd-loaded PPF catalyst can be separated and reused over five times without significant loss of catalytic performance and selectivity for the cycloaddition of CO2 to epoxides. This intuitively appealing methodology tolerates a wide variety of functional groups and opens an avenue for Pd-based imine-linked frameworks as a reliable platform to control regioselectivity. [ABSTRACT FROM AUTHOR]

We described the protein engineering of the halohydrin dehalogenase HheG to enhance its R enantioselectivity for the synthesis of chiral 4‐aryloxazolidinones via α‐regioselective ring‐opening of aryl epoxides with cyanate. Additionally, we achieved the inversion of its regioselectivity and enantioselectivity, resulting in a HheG variant tailored for the synthesis of chiral 5‐aryloxazolidinones via β‐regioselective and S‐enantioselective ring‐opening of aryl epoxides with cyanate. Leveraging these engineered mutants, we developed a biocatalytic platform capable of synthesis of both chiral 4‐aryloxazolidinones (up to 47% yield, 98% ee, and 99% regioselectivity) and chiral 5‐aryloxazolidinones (up to 46% yield, >99% ee, and 98% regioselectivity). Furthermore, a collaborative approach utilizing two regio‐ and enantioselective HheG mutants has been demonstrated to enable the simultaneous synthesis of chiral 4‐aryloxazolidinones and chiral 5‐aryloxazolidinones. [ABSTRACT FROM AUTHOR]

This article presents a new method for synthesizing α-quaternary carbaldehydes through the chemoselective House-Meinwald rearrangement of trisubstituted epoxides. The authors used Brønsted acids as catalysts and identified optimal reaction conditions. The method allows for the synthesis of various carbaldehydes and has been validated for stereospecific reactions. The authors suggest that this method could be useful in the total synthesis of natural products. [Extracted from the article]

The synthesis of bio‐derived cyclic carbonates is attracting a lot of attention as the incorporation of bio‐derived functionality into these compounds provides the opportunity to prepare previously unknown structures, whilst also improving their sustainability profiles. This study presents a facile preparation of diastereomerically pure bio‐derived cyclic carbonates displaying a range of optical rotation values. These compounds are obtained from glycidol, amino acids and CO2 in a facile two‐step approach. Initially, the diastereomerically pure amino acid functionalised epoxides are prepared through a robust Steglich esterification of enantiopure glycidol (R or S) and an amino acid (D or L). Thereafter, in a second step, cycloaddition of the epoxide with CO2 results in the retention of the initial stereochemistry of the epoxide, furnishing novel diastereomerically pure and optically active cyclic carbonate products. A DFT study has explained the basis of this observed retention of configuration for these compounds. Further, results from this DFT study also provide new mechanistic information concerning a co‐catalyst‐free cycloaddition reaction starting from glycidol when using the gallium‐catalyst, which is found to operate through metal‐ligand cooperativity. [ABSTRACT FROM AUTHOR]

The in-line control of curing during the molding process significantly improves product quality and ensures the reliability of packaging materials with the required thermo-mechanical and adhesion properties. The choice of the morphological and thermo-mechanical properties of the molded material, and the accuracy of their determination through carefully selected thermo-analytical methods, play a crucial role in the qualitative prediction of trends in packaging product properties as process parameters are varied. This work aimed to verify the quality of the models and their validation using a highly filled molding resin with an identical chemical composition but 10 wt% difference in silica particles (SPs). Morphological and mechanical material properties were determined by dielectric analysis (DEA), differential scanning calorimetry (DSC), warpage analysis and dynamic mechanical analysis (DMA). The effects of temperature and injection speed on the morphological properties were analyzed through the design of experiments (DoE) and illustrated by response surface plots. A comprehensive approach to monitor the evolution of ionic viscosity (IV), residual enthalpy (dHrest), glass transition temperature (Tg), and storage modulus (E) as a function of the transfer-mold process parameters and post-mold-cure (PMC) conditions of the material was established. The reliability of Tg estimation was tested using two methods: warpage analysis and DMA. The noticeable deterioration in the quality of the analytical signal for highly filled materials at high cure rates is discussed. Controlling the temperature by increasing the injection speed leads to the formation of a polymer network with a lower Tg and an increased storage modulus, indicating a lower density and a more heterogeneous structure due to the high heating rate and shear heating effect. [ABSTRACT FROM AUTHOR]

A facile metalation of Schiff base organic polymer, Te-TETA obtained from terephthalaldehyde and triethylenetetramine, with zinc to produce metalated organic polymer, Te-TETA-Zn has been reported here. Both Te-TETA and Te-TETA-Zn were analyzed by various analytical techniques viz. FT-IR, PXRD, FE-SEM, EDX, XPS, TGA and BET. Further, HR-TEM images of metalated organic polymer, Te-TETA-Zn was also recorded. EDX and XPS analyses clearly revealed the metalation of Zn in the organic polymer. Further, a huge transformation from the spherical morphology of Te-TETA to the flattened structure in Te-TETA-Zn can be seen in the FE-SEM and TEM images endorsing the successful coordination of zinc with the N-coordinating sites. An investigation of the catalytic activity of Te-TETA-Zn in combination with tetrabutylammonium bromide (TBAB, 2 mol%) reveals it to be an efficient heterogeneous catalyst component for the chemical fixation of CO2 to epoxides producing cyclic carbonate products (up to 99% conversion) under reaction conditions [Te-TETA-Zn (20 mg), TBAB (2 mol%), 5 bar CO2 pressure, 60 °C, 4 h]. [ABSTRACT FROM AUTHOR]

This comparative study experimentally investigates the effect of both the type and content of carbon based nanoparticles on the mechanical properties of epoxy composites. For this purpose, carbon nanotubes (CNTs), expanded graphite (EG), and carbon black (CB) were used as reinforcing nanoparticles at various concentrations within the epoxy polymer. The nanoparticles were dispersed by ultrasonication method. CNTs incorporated up to 0.4% by weight (wt.) while EG and CB nanoparticles were employed at 4%, 8%, 10%, and 12% concentrations by weight. Tensile tests of the nanocomposites were conducted according to ASTM D680 to determine the mechanical properties of nanocomposites including ultimate tensile strength and modulus. The results revealed that all types of nanoparticles have a strong reinforcing effect on the mechanical properties depending on their concentrations. When carbon nanotubes (CNTs) were used, the highest improvement in strength, by 84.7% at 0.1% wt., and in modulus, by 32.1% at 0.2% wt. content, was observed. EG nanoparticles exhibited improvement in both strength and modulus at all contents. The highest improvement in strength, by 109.6% at 4% wt., and in modulus, by 95.6% at 10% wt. concentration, was observed. In the case of carbon black (CB), improvement in strength was observed only at 4% wt. concentration, by 44.9%. On the other hand, enhancement in modulus was seen at all CB contents, with the greatest improvement at 10% wt., reaching 58.2%. [ABSTRACT FROM AUTHOR]

In this research work, we have designed and introduced [Zr-UiO-66-CO2H]Br as a versatile heterogeneous acid catalyst for the ring-opening of epoxides through SN1 and/or SN2 type mechanisms. In addition, the appropriate method for designing an active and efficient Bronsted acid site in metal-organic frameworks is discussed. [Zr-UiO-66-CO2H]Br was applied for the preparation of α-aryloxy alcohols by the condensation reaction of various epoxides with phenol or thiophenols under mild and green conditions. [ABSTRACT FROM AUTHOR]

Polyamide 6 (PA6) is a widely used thermoplastic engineering polymer, and the toughening modification for PA6 is always a main research topic. Meanwhile, the rigidity and heat resistance of PA6 usually deteriorate. To address this conflict, an epoxy compound (EGDE‐GA) was designed and synthesized and used to modify PA6 by dynamic vulcanization in twin‐screw extruder. EGDE‐GA is a linear molecule with a flexible molecular structure, which is favorable to toughening of PA6, and epoxy groups of EGDE‐GA can form local cross‐linked structure to improve the rigidity and retain the heat resistance of PA6. At the loading of 20 wt% of EGDE‐GA, the modified PA6 (PA6/EGDE‐GA 20) exhibited very high elongation at break and notched impact strength, which were increased by 413% and 520%, respectively, compared to those of PA6. The tensile strength was 61.4 MPa, which was higher than that of PA6. The heat deflection temperature remained almost unchanged. The results showed that the modified polymers may possess the high toughness without sacrificing the original rigidity by building the local crosslinked structure using dynamic vulcanization. The findings provide a feasible method for reusing and upcycling PA6 and other polymers with higher value and wider use in the industry. Highlights: The polyamide 6 (PA6) is toughened via dynamic vulcanization.The toughness of modified PA6 is increased by 520% compared with pure PA6.The toughened PA6 exhibits higher tensile strength than that of pure PA6.The toughened PA6 maintains its rigidity and heat resistance. [ABSTRACT FROM AUTHOR]

The design of molecular scaffolds bearing multiple functional groups for the activation and ring‐opening of epoxides is a crucial challenge for the synthesis of efficient homogeneous and heterogeneous catalysts that are used for the cycloaddition reaction of CO2 to epoxides. Traditional approaches to prepare such multifunctional catalysts often imply multistep synthetic procedures and expensive building blocks. In this work we show that bifunctional catalysts for the cycloaddition of CO2 to epoxides bearing a Lewis acid metal and a quaternary ammonium halide group can be prepared in just two steps starting from an opportunely designed epoxide precursor by using inexpensive substrates. Such a readily accessible catalyst was applied for the cycloaddition of CO2 to a series of epoxides under atmospheric conditions generally leading to quantitative substrate conversion and high carbonate selectivities. Importantly, we also show that the epoxide‐driven concept developed for the preparation of the molecular catalyst, could be applied to prepare recyclable heterogeneous systems for the target cycloaddition reaction. [ABSTRACT FROM AUTHOR]

This article explores the regioselectivity during the formation of aminoboronates from epoxides. The researchers aimed to investigate the stability of unprotected α-boryl aziridines and the effect of B-N interaction on their stability. They successfully isolated aziridine MIDA boronate through the Staudinger reaction and discovered a rare case of a geminal azidoalcohol. The researchers also attempted to synthesize the desired azidoalcohol through different approaches but were unsuccessful. The synthesis of unprotected aziridine MIDA boronate provides a useful building block for further transformations. [Extracted from the article]

The cycloaddition of CO2 to epoxides to afford versatile and useful cyclic carbonate compounds is a highly investigated method for the nonreductive upcycling of CO2. One of the main focuses of the current research in this area is the discovery of readily available, sustainable, and inexpensive catalysts, and of catalytic methodologies that allow their seamless solvent-free recycling. Water, often regarded as an undesirable pollutant in the cycloaddition process, is progressively emerging as a helpful reaction component. On the one hand, it serves as an inexpensive hydrogen bond donor (HBD) to enhance the performance of ionic compounds; on the other hand, aqueous media allow the development of diverse catalytic protocols that can boost catalytic performance or ease the recycling of molecular catalysts. An overview of the advances in the use of aqueous and biphasic aqueous systems for the cycloaddition of CO2 to epoxides is provided in this work along with recommendations for possible future developments. [ABSTRACT FROM AUTHOR]

Cyclic carbonates are often produced through catalytic coupling reactions of CO2 with epoxides under harsh conditions. Here, we present a highly active nanoporous copper (np‐Cu) cathode material for the electrosynthesis of cyclic carbonates in mild environments. Np−Cu material was drop casted on glassy carbon (np‐Cu/GC) as cathode electrode to perform galvanostatic electrosynthesis using a magnesium anode in CO2‐saturated acetonitrile with 0.1 M tetraethylammonium iodide. Very good yields have been obtained for 1,2‐butylene carbonate (BC, 74 ± 4 %) and propylene carbonate (PC, 62 ± 6 %). By varying the cathode electrode materials, low yields (≤ 20 %) on bare GC, but similar yields (76 ± 4 % BC and 63 ± 5 % PC) on polycrystalline Cu were achieved. Although the pore‐ligament structure is beneficial to enhance the CO2RR performance, its impact on the yield of cyclic carbonate is minimal. This implies that the activation of CO2 to the CO2⋅− radical anion is not the rate‐limiting step, but rather the ring closure of the final intermediate to form cyclic carbonates. Moreover, the np‐Cu/GC shows very good stability and reusability for the electrochemical‐organic test reaction. This study provides deeper insights into the reaction mechanism of cyclic carbonates formation on Cu‐based electrodes. [ABSTRACT FROM AUTHOR]

Palm oil contains an abundant concentration of oleic acid which is known to have low toxicity to human health. The unsaturated double‐bond structure in oleic acid can be modified to synthesize oleate epoxides. The potential benefit of epoxide derivatives is their high biological activity that can be directed as new anticancer agents. In this work, the synthesis of epoxides from purified fatty acid methyl ester (EPFAME) and epoxides from purified fatty acid ethyl ester (EPFAEE) from palm oil in addition to cytotoxicity evaluations as new anticancer agents were investigated by in vitro and in silico studies. Both EPFAME and EPFAEE derivatives were successfully obtained in 82.80 % and 85.80 % yield, respectively. The MTT assay results revealed that EPFAME and EPFAEE significantly decreased the cell viability of WiDr cancer cells with IC50 of 2.70 and 14.23 μg/mL, respectively. They also showed moderate potency against T47D and HeLa cancer cell lines with IC50≥20 μg/mL. The results suggested that the addition of a methylene group from EPFAME to EPFAEE lowers cytotoxicity. A molecular docking study revealed that EPFAME and EPFAEE bind to the fatty acid synthase (FASN) protein interacting with high stability. This is represented by the binding affinity values of EPFAME and EPFAEE to FASN protein which are −7.3 and −8.1 kcal/mol, respectively. Using epoxide compounds derived from palm oil, fatty acid esters were shown to have potential medical benefits due to their low cytotoxicity and anticancer agency against several cell lines by inhibiting proliferation and inducing apoptosis of cancer cells. [ABSTRACT FROM AUTHOR]

Over past few decades, synthetic chemists are working tirelessly for the development of environmentally benign and economically competent carbon‐oxygen bond formation processes. Various oxidizing reagents and catalysts are being used to serve this purpose. Among all, t‐butyl hydrogen peroxide (TBHP) has emerged as a greener and economically viable oxygen source, radical initiator and precursor of t‐BuO⋅ and t‐BuOO⋅ radicals. It has been extensively utilized as a reagent for the synthesis of epoxides, ketones, secondary alcohols, heterocyclic rings like benzofurans, isoquinoline and many more. The present review will unfold the recent advancements made in the field of TBHP‐promoted C−O bond formation. [ABSTRACT FROM AUTHOR]

A concise synthesis of the sex pheromones of elm spanworm as well as painted apple moth has been achieved. The key steps were the alkylation of acetylide ion, Sharpless asymmetric epoxidation and Brown's P2-Ni reduction. This approach provided the sex pheromone of the elm spanworm (1) in 31% total yield and those of the painted apple moth (2, 3) in 26% and 32% total yields. The ee values of three final products were up to 99%. The synthesized pheromones hold promising potential for use in the management and control of these pests. [ABSTRACT FROM AUTHOR]

The ring opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is one of the most important ways to synthesize polyesters both in industrial and academic fields. Herein, the zeolitic imidazolate framework‐67 (ZIF‐67) was used as a heterogeneous catalyst for the ROCOP of epoxides and cyclic anhydrides without co‐catalyst and initiator. Notably, the obtained polyesters with alternate structures were proved by the 1H NMR spectrum and FTIR spectrum, which indicate the ROCOP is alternatively copolymerized. Kinetic study of the ROCOP of cyclohexene oxide (CHO) and phthalic anhydride (PA) shows that the polymerization reaction is first‐order kinetics. The apparent activation energy (Ea) of the ROCOP of CHO and PA catalyzed by ZIF‐67 was found to be about 104.4 KJ/mol. A possible mechanism of ROCOP of CHO and PA is that the metal Co coordinates with the oxygen atom on the monomer to weaken the C‐O bond thereby opening the ring structure and initiating the copolymerization reaction. In this study, a new system for the copolymerization of epoxide and anhydride catalyzed by heterogeneous catalysts was discovered, which has important guiding significance. [ABSTRACT FROM AUTHOR]

Dense multi-cationic Sm-Co-O, Sm-Ni-O, Al-Co-O, Al-Ni-O, and Al-Ni-Co-O oxide aerogels were prepared by epoxide-driven sol–gel synthesis. Catalysts for dry reformation of methane, Sm2O3/Co, Sm2O3/Ni, Al2O3/Co, Al2O3/Ni, Al2O3/Co, and Ni were prepared by reduction of aerogels with hydrogen and their catalytic activities and C-deposition during dry reformation of methane were tested. Catalytic tests showed high methane conversion (93–98%) and C-deposition (0.01–4.35 mg C/gcat.h). The highest content of C-deposits after catalytic tests was determined for Al2O3/Co and Al2O3/Ni catalysts, which was related to the formation of Al alloys with Co and Ni. A uniform distribution of Co0 and Ni0 nanoparticles (in the form of a CoNi alloy) was found only for the Al2O3/Co and Ni catalysts, which showed the highest activity as well as low C deposition. [ABSTRACT FROM AUTHOR]

Bitumen emulsion faces the major concern of low mechanical strength, especially at high service temperatures. To improve the mechanical performance of bitumen emulsion, waterborne epoxy resin was used as a modifier in this study. The effects of waterborne epoxy resin on the fatigue performance of bitumen emulsion were evaluated in this study using both the stress-controlled time sweep test and linear amplitude (LAS) test. The dissipated energy concept and viscoelastic continuum damage (VECD) theory were adopted to analyze the fatigue testing data obtained from the time sweep test and LAS test, respectively. It is found that the fatigue life of the emulsion residues increased with the incorporation of waterborne epoxy resin from the time sweep test conducted at the stress levels from 300 kPa to 500 kPa. On the other hand, the LAS test indicated that the trend of the predicted fatigue life of the emulsion residues was strain dependent. [ABSTRACT FROM AUTHOR]

A stereospecific deoxygenation of trans‐epoxy cinnamic acid derivatives to access (Z)‐cinnamamides, (Z)‐cinnamyl alcohol and (Z)‐cinnamyl amines using a catalytic system based on nickel triflate and triphenylphosphine has been developed. The desired products were obtained in good to excellent yield (up to 92 % isolated yield) and excellent stereospecificity (Z : E ratio up to>99 : 1). The transformation has a broad functional group tolerance including amides, amines, alcohols and esters. The power of the methodology was demonstrated in the key step of the total synthesis of biologically active natural product, N‐cis‐feruloyl tyramine from readily available trans‐ferulic acid. A reaction mechanism involving activation of epoxide via coordination of the oxygen atom and the neighboring O‐ or N‐atoms to the nickel catalyst and formation of Ph3P‐carbon bond is proposed. This method is important for synthesis of highly desirable functionalized (Z)‐alkenes from readily available (E)‐alkenes. [ABSTRACT FROM AUTHOR]