Latest ArticlesIn this work, we established an exceptionally facile method for the preparation of Ni-CeO2 nanorods in a kind of deep eutectic solvents (DESs) composed of L-proline and Ce(NO3)3·6H2O. First, Ni-CeO2 nanorods were successfully prepared by adding Ni(NO3)3·6H2O to DESs. Then, we found that Ni-CeO2 nanorods prepared in DESs have more prominent oxidase-like activity than pure CeO2. The outstanding catalytic activity of Ni-CeO2 could be ascribed to its high Ce3+/Ce4+ ratio. As a proof-of-concept application, the Ni-CeO2 nanorods were successfully acted as a colorimetric platform for the sensitive determination of ascorbic acid and α-glucosidase activity, which displays excellent analytical performance. Moreover, this sensing platform was applied for screening natural α-glucosidase inhibitors, such as terpenoids from natural products. The results indicated that ursolic acid and oleanolic acid had good inhibitory rates. This strategy not only provides a new way to construct more kinds of nanomaterials from DESs, but also offers a facile and effective tool to screen the α-glucosidase natural inhibitors as potential anti-diabetic drugs.
In this study, a series of arylene-bridged bis(benzimidazolium)triflates 1–62+·2[OTf–] were synthesized by grafting different π-linkers with benzimidazolium scaffolds. Among them, compound 12+·2[OTf–] with anthracene as the linker exhibited remarkable electron transfer capabilities across four distinct redox states. The inclusion of an anthracene unit as the π-linker contributes to its exceptional redox and optoelectronic characteristics. Consequently, 12+·2[OTf–] was successfully utilized as both an electrochromic molecule in an ECD under applied voltage for the first time, and a highly efficient photocatalyst for the formation of carbon–phosphorus bonds via visible-light-induced cross-dehydrogenative coupling reactions.
Catalytic C-H activation-initiated annulation reactions have emerged as a versatile strategy for the efficient construction of diverse ring structural units and complex cyclic molecules in synthetic chemistry. Herein, we describe a new Rh(Ⅲ)-catalyzed C-H activation-initiated transdiannulation reaction of N, N-dimethyl enaminones with gem-difluorocyclopropenes in the presence of H2O, enabling a facile and oxygen transfer access to ring-fluorinated tricyclic γ-lactones with a 6-5 ring-junction tetrasubstituted stereocenter. This approach features bond-forming/annulation efficiency, good functional group tolerance and complete regioselectivity, which may include a complex process consisting of Rh(Ⅲ)-catalyzed C(sp2)H activation, cyclic alkene insertion, defluorinated ring-opening of gem-difluorocyclopropane, intramolecular oxygen transfer, intramolecular cyclization and oxidative hydration.
Enones are widely explored in synthetic chemistry as fundamental building blocks for a wide range of reactions and exhibit intriguing biological activities that are pivotal for drug discovery. The development of synthetic strategies for highly efficient preparation of enones thereby receives intense attention, in particular through the transition metal-catalyzed coupling reactions. Here, we describe a carbene-catalyzed cross dehydrogenative coupling (CDC) reaction that enables effective assembly of simple aldehydes and alkenes to afford a diverse set of enone derivatives. Mechanistically, the in situ generated aryl radical is pivotal to "activate" the alkene by forming an allyl radical through intermolecular hydrogen atom transfer (HAT) pathway and thus forging the carbon-carbon bond formation with aldehyde as the acyl synthon. Notably, our method represents the first example on the enone synthesis through coupling of "non-functionalized" aldehydes and alkenes as coupling partners, and offers a distinct organocatalytic pathway to the transition metal-catalyzed coupling transformations.
In the quest for new agrochemicals and pharmaceuticals, chemists seek access to reliable and mild synthetic techniques to allow for the systematic modification of chemical structures, exploration of unexplored chemical space, and facilitation of practical synthesis in their search for novel agrochemicals and pharmaceuticals. In this regard, photocatalytic reactions enabled the synthesis of intricate and more functionalized compounds. This review overviews the developed synthetic methodologies and their utility in the chemical synthesis of pharmaceuticals. This review also offers in-depth insights into contemporary photoredox reactions such as allylic additions, cyclization, reductive cross-coupling, CH activation, ring opening, oxidative cross-coupling, dehydrogenation, desulphonation, and decarboxylation. It provides a positive outlook for the promising future of this field.
A highly site-selective intermolecular trifluoromethylimination of activated and unactivated olefins was reported under transition-metal- and photosensitizer-free conditions. This newly developed strategy provides straightforward and efficient access to diverse value-added vicinal trifluoromethyl amines without resorting to the pre-functionalized reagents. Mechanistic experiments demonstrate that the approach proceeded through CF3 and iminyl two-radicals process, which were generated directly from commercially available benzophenone imine in a novel electron-donor mode via a SET process activated by the bifunctional hypervalent iodine reagents. The synthetic potential of the protocols was further showcased via the condensation/amination sequential cascade, and transformations to access β-CF3 primary amines.
Photosynthesis is the process through which living plants utilize photosynthetic pigments, such as chlorophyll, to convert CO2 and water into organic compounds and release O2 under visible light. In this study, we have successfully constructed a fluorescent supramolecular polymer (P5Py2/Zn/Gen)n by employing orthogonal pillar[5]arene-based molecular recognition and metal ion coordination. Within the supramolecular polymer, the guest molecule Gen unit acts as a light-harvesting moiety, as the ACQ effect is inhibited by host-guest interactions, while the (Py)2/Zn center serves as a catalytic site. By employing this orthogonal self-assembly strategy, we have enhanced the stability of both the donor and acceptor in catalyzing the reduction of p-nitrophenol to p-aminophenol. Moreover, this photocatalyst can be reused at least 5 times without significant conversion loss. These findings provide a pathway for constructing a recyclable artificial LHS that mimics the entire photosynthesis process.
A simple and additive-free protocol has been developed for the preparation of β-keto phosphorodithioates through the three-component reaction of easily available sulfoxonium ylides, P4S10, and alcohols. The present geminal hydro-phosphorodithiolation reaction was performed at room temperature to construct a series of β-keto phosphorodithioates in the absence of any metal reagents, bases, or additives.
In recent years, FeCl3-photocatalyzed direct C–H/Si–H bond functionalization reactions have attracted huge attention. In those transformations, chlorine radical (Cl•) could be generated from FeCl3 via a ligand-to-metal charge transfer (LMCT)/homolysis process under light irradiation. The resulting chlorine radical subsequently acts as a hydrogen atom transfer (HAT) agent to abstract the hydrogen atom of aliphatic C–H, O–H, or Si–H bonds to give the corresponding C/Si/O-centered radicals for various organic transformations. In this review, we summarized the recent advances in the application of FeCl3 as a HAT photocatalyst for the C/Si–H functionalization to construct C–C, C–N, C–Si, C–S, C–B, and C-P bonds.
A rhodium(Ⅲ)-catalyzed hydrosilylation/cyclization reaction of cyclohexadienone-tethered α, β-unsaturated aldehydes (1, 6-dienes) with triethylsilane is described, providing a series of cis-hydrobenzofurans, cis-hydroindoles, and cis-hydroindenes bearing silyl enol ether in good to excellent yields and excellent stereoselectivities. Additionally, the versatility of this method was demonstrated through a gram-scale experiment and various downstream transformations, highlighting its utility.
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