Recent progress of metal halide perovskite materials in heterogeneous photocatalytic organic reactions.

Photocatalytic technology is widely regarded as an important way to utilize solar energy and achieve carbon neutrality, which has attracted considerable attentions in various fields over the past decades. Metal halide perovskites (MHPs) are recognized as "superstar" materials due to their exceptional photoelectric properties, readily accessible and tunable structure, which made them intensively studied in solar cells, light-emitting diodes, and solar energy conversion fields. Since 2018, increased attention has been focused on applying the MHPs as a heterogeneous visible light photocatalyst in catalyzing organic synthesis reactions. In this review, we present an overview of photocatalytic technology and principles of heterogeneous photocatalysis before delving into the structural characteristics, stability, and classifications of MHPs. We then focus on recent developments of MHPs in photocatalyzing various organic synthesis reactions, such as oxidation, cyclization, C-C coupling etc., based on their classifications and reported reaction types. Finally, we discuss the main limitations and prospects regarding the application of metal halide perovskites in organic synthesis.

Solvent-regulated self-assembled carbon nitride for photocatalytic reduction of U(VI) in water.

Manufacturing high-performance and reusable materials from radioactive uranium-containing wastewater remains a significant challenge. Herein, a supramolecular self-assembly strategy was proposed, using melamine and cyanuric acid as precursors and using intermolecular hydrogen bond force to form carbon nitride (CN-D) in different solvents through a single thermal polymerization strategy. Supramolecular self-assembly method is a promising strategy to synthesize a novel carbon nitride with molecular regulatory properties. In addition, 98% of U(VI) in wastewater can be removed by using CN-D for 60 min under visible light. After five cycles of recycling, more than 95% of U(VI) can still be reduced, indicating that it has good recyclability and reusability. This study not only provides an efficient photocatalytic method of uranium reduction, but also provides a new method for self-assembly synthesis.

Visible-light-induced decarboxylative cascade cyclization of acryloylbenzamides with N-hydroxyphthalimide esters via EDA complexes.

A visible-light-induced decarboxylative cascade reaction of acryloylbenzamides with alkyl N-hydroxyphthalimide (NHP) esters for the synthesis of various 4-alkyl isoquinolinediones mediated by triphenylphosphine (PPh3) and sodium iodide (NaI) was developed. This operationally simple protocol proceeded via the photoactivation of electron donor-acceptor (EDA) complexes between N-hydroxyphthalimide esters and NaI/PPh3, resulting in multiple carbon-carbon bond formations without the use of precious metal complexes or synthetically elaborate organic dyes, which provided an alternative practical approach to synthesize diverse isoquinoline-1,3(2H,4H)-dione derivatives.

Visible light-mediated synthesis of quinazolinones from benzyl bromides and 2-aminobenzamides without using any photocatalyst or additive.

This paper reports a novel method for the visible-light-mediated synthesis of quinazolinones from the reaction of benzyl bromides with 2-aminobenzamides. The reaction proceeded efficiently at room temperature upon irradiation with an 18 W blue light-emitting diode in air without photocatalysts or additives. By varying the solvent type, substrate molar ratio, and reaction time, the optimal reaction conditions, including the use of methanol solvent, room temperature, and reaction time of 28 h, were identified. Under these conditions, various quinazolinones were obtained using 18 substrates, with the highest yield of 93%. To determine the industrial value of the proposed method, a scale-up reaction was performed and 80% product yield was achieved. Mechanistic studies revealed that the reaction likely proceeded via a radical pathway and that the hydrogen bromide by-product generated during the first step of the reaction of benzyl bromide with 2-aminobenzamide promoted the subsequent step.

Visible-Light Photocatalytic Highly Selective Oxidation of Alcohols into Carbonyl Compounds by CsPbBr3 Perovskite.

Conversion of alcohols into corresponding carbonyl compounds through an oxidation reaction with high conversion and selectivity simultaneously under mild conditions still remains a great challenge. Herein, a cost-effective and highly efficient photocatalytic protocol for selective oxidation of alcohols was developed using CsPbBr3 perovskite as a heterogeneous photocatalyst, which afforded aldehydes/ketones exclusively with a yield of 99% at ambient temperature under an air atmosphere. Moreover, the photocatalyst can be recycled at least 5 times without a significant decrease in catalytic activity. The detailed reaction mechanism was investigated by a series of quenching experiments, including Stern-Volmer experiments and electron paramagnetic resonance spectroscopy analysis as well as DFT calculations.

Visible-Light Photocatalytic Aerobic C═C Bond Cleavage of Alkenes to Carbonyls by CsPbBr3 Nanocrystals.

Herein, we reported a facile and readily accessible visible-light-driven photocatalytic protocol to induce oxidative cleavage of C═C bonds to corresponding carbonyls using CsPbBr3 nanocrystals as photocatalysts. This catalytic system was applicable to a wide range of terminal and internal alkenes. Detailed mechanism studies indicated that a single-electron transfer (SET) process was involved in this transformation, wherein the superoxide radical (O2•-) and photogenerated holes played crucial roles. Additionally, DFT calculations revealed that the reaction was initiated by the addition of O2•- to the terminal carbon atom of the C═C bond and completed by releasing one molecular formaldehyde by the formed [2 + 2] intermediate; the latter conversion was a rate-determining process.

Fast quinazolinone synthesis by combining enzymatic catalysis and photocatalysis.

A fast and highly efficient method for the synthesis of functionalized quinazolinones by combining enzymatic catalysis and photocatalysis is reported. The α-Chymotrypsin catalyzed the cyclization of aldehyde and 2-aminobenzamide, which was subsequently followed by White LED-induced oxidation of 2-phenyl-2, 3-dihydroquinazolin-4(1H)-one to obtain quinazolinone. The reaction process was highly efficient with a reaction yield of 99% in just 2 h, and a wide range of quinazolinones could be synthesized. Furthermore, the plausible mechanism was investigated by control experiments and DFT calculations. This protocol provides an alternative synthetic route for the preparation of quinazolinone derivatives.

MIL-100(Fe)/g-C3N4 composites with enhanced photocatalytic activity for UO22+ reduction under visible light.

As a clean energy source, nuclear energy can gradually replace traditional fossil energy sources, and is an important means to achieve the "double carbon goal". Uranium-containing wastewater is inevitable in the development of nuclear energy. The composites MIL/CNx of MOF material MIL-100(Fe) and carbon nitride (CN) were obtained by a simple solvo-thermal method using iron nitrate, homophthalic acid and CN. The material MIL-100(Fe) with high specific surface area was compounded with CN to increase the in-plane adsorption sites, which could adsorb 30% of uranium in solution during the dark reaction. The close interfacial contact of the two materials effectively inhibited the complexation of photo-generated electrons and holes and promotes electron migration. These two synergistic effects improved their overall photocatalytic reduction capacity, which could reduce 97% of UO22+ in solution in 20 min. The UO22+ removal efficiency of MIL/CN0.1 was 2.3 and 1.6 times higher than that of CN and MIL-100(Fe), respectively. In addition, MIL/CN0.1 was stable in reducing uranium during the five cycles of the experiment.

Synthesis of fused quinazolinones via visible light induced cyclization of 2-aminobenzaldehydes with tetrahydroisoquinolines.

This study reports a novel method for the synthesis of fused quinazolinones by visible-light-induced cyclization of 2-aminobenzaldehydes and tetrahydroisoquinolines. The reaction is easily carried out by irradiation with a blue LED in the presence of 9-fluorenone and air. A broad substrate scope with good tolerance of functionalities was observed under the optimized reaction conditions. Moreover, using 2-aminophenone as the substrate and under similar reaction conditions, the same product was obtained when a carbon was removed. The bio-active naturally occurring alkaloid rutaecarpine could be obtained by this strategy. The success of the reaction on the gram-scale and the further transformation of the substrate demonstrated the synthetic practicability of this reaction.

Combining Enzyme and Photoredox Catalysis for the Construction of 3-Aminoalkyl Chromones.

Herein, we reported a practical and efficient strategy combining photoredox and enzyme catalysis for the construction of 3-aminoalkyl chromones from o-hydroxyaryl enaminones and N-arylglycine esters. A variety of 3-aminoalkyl chromones were synthesized with good yields under mild conditions in one pot. This synthetic protocol consists of sequential enzymatic hydrolysis and photoredox decarboxylation of N-arylglycine esters, oxidation of aminoalkyl radicals, Mannich reaction, and intramolecular nucleophilic cyclization, which affords a convenient pathway for the preparation of various 3-substituted chromones.

Synthesis of quinazoline by decarboxylation of 2-aminobenzylamine and α-keto acid under visible light catalysis.

Quinazoline compounds demonstrate a variety of physiological and pharmacological activities. However, the most common syntheses require large quantities of oxidants, high temperature, and other extreme conditions. In this study, quinazoline compounds were synthesized from the condensation of α-keto acid and 2-aminobenzylamine and then decarboxylation under blue LED irradiation at room temperature without transition metal catalysts or additives. Therefore, we demonstrated that by using α-keto acid as the acyl source, decarboxylation can be realized under blue LED without oxidants, in a simple, mild, and environmentally friendly process.

Base-promoted synthesis of diarylsulfones from sulfonyl hydrazines and diaryliodonium salts.

An efficient and concise method for the synthesis of diverse substituted sulfones was developed with high selectivity. Using n-PrOH as the solvent, diaryl sulfones are formed even on a gram scale via metal-free coupling from sulfonyl hydrazines with symmetrical or unsymmetrical diaryliodonium salts.

Photocatalyst-free visible-light-promoted quinazolinone synthesis at room temperature utilizing aldehydes generated in situ via C[double bond, length as m-dash]C bond cleavage.

This is the first report on a facile tandem route for synthesizing quinazolinones at room temperature from various aminobenzamides and in situ-generated aldehydes. The latter was formed via C[double bond, length as m-dash]C bond cleavage, and the overall reaction proceeded using molecular oxygen as a clean oxidant in the absence of a photocatalyst. Visible light, which was indispensable for the entire course of the reaction, played multiple roles. It initially cleaved styrene to an aldehyde, then facilitated its cyclization with an o-substituted aniline, and finally promoted the dehydrogenation of the cyclized intermediate. The previous step provided the feedstock for the next step in the reaction, thereby preventing volatilization, oxidation, and polymerization of the aldehyde. Thus, the overall process is simple, environmentally benign, and economically feasible.

Visible-Light-Induced Dehydrogenative Imidoylation of Imidazo[1,2-a]pyridines with α-Amino Acid Derivatives and α-Amino Ketones.

A new and efficient visible-light-promoted dehydrogenative cross-coupling reaction of imidazo[1,2-a]pyridines with α-amino carbonyl compounds toward imidoyl imidazo[1,2-a]pyridines is developed. A diverse range of imidazo[1,2-a]pyridines undergoes the dehydrogenative imidoylation smoothly with α-amino carbonyl compounds to access the corresponding products in satisfactory yields. We have also proposed the possible reaction mechanism based on preliminary mechanistic studies. The synthetic method has the advantages of wide substrate scope, good functional tolerance, and mild reaction conditions, which make this transformation more practical and sustainable.

Synthesis of Mannich-type derivatives from amides activated by hydrogen bonding with ZnCl2.

The amide group has one of the most significant functionalities found in many natural products. Herein, low-nucleophilic amides are used in a Mannich-type reaction to synthesize N-acyl-protected amine derivatives. A highly efficient synthetic method utilizing simple aldehydes, N-substituted anilines, and amides as substrates was established through a one-pot amide pathway activated by hydrogen bonding between the ZnCl2 and amide under solvent-free conditions. This strategy can be broadly applied to medicinal chemistry. More importantly, compared with the previous Lewis acid catalyzed reaction, we proposed a new application of zinc chloride.

Efficient biocatalytic strategy for one-pot Biginelli reaction via enhanced specific effects of microwave in a circulating reactor.

A one-pot efficient biocatalytic strategy for the synthesis of 3,4-dihydropyrimidin-2-(1H)-ones was developed in a circulating microwave reactor selecting α-chymotrypsin as the promiscuous biocatalyst. In the circulating reaction system, the combination of microwave heating and external cooling could avoid the denaturation and inactivation of enzyme, and greatly improved the radiation power of microwave, thus improving the specific effects of microwave. During the reaction process, the microwave radiation power was automatically adjusted by adjusting the speed of the reaction mixture circulation. When the microwave power was maintained at 110 W, the best results could be obtained with the highest yield of 96% at 55 °C in 50 min, and the reaction had a wide range of substrates. But no obvious product was detected in a tank microwave reactor at 55 °C for 100 min, under this condition, the microwave power was maintained at about 3 W. As a contrast, the reaction only obtained 63% yield in 55 °C oil bath for 96 h.

Cobalt-Catalyzed Oxidative Phosphonylation of α-Amino Acid Derivatives and α-Amino Ketones for α-Aminophosphonates.

A novel and efficient direct oxidative phosphonylation of α-amino ketones and α-amino acid derivatives with dialkyl phosphites by the catalysis of a cobalt salt under air is disclosed. A variety of α-amino ketones and α-amino acid derivatives underwent the reaction well with dialkyl phosphites to produce the desired α-aminophosphonates. This protocol not only provides an alternative synthetic route for the preparation of diverse α-aminophosphonates but also avoids the use of potentially explosive peroxide agents.

Ionic Liquid as an Efficient Medium for the Synthesis of Quinoline Derivatives via α-Chymotrypsin-Catalyzed Friedländer Condensation.

An efficient, convenient, and eco-friendly biocatalytic approach was developed for the synthesis of quinoline derivatives via the α-chymotrypsin-catalyzed Friedländer reaction. Interestingly, α-chymotrypsin exhibited higher catalytic activity in an ionic liquid (IL) aqueous solution as compared to that observed in our previous relevant study, which was conducted using an organic solvent, and a series of substrates gave similar excellent yields at lower reaction temperature and under reduced enzyme-loading conditions.

Copper-Catalyzed Aerobic Cascade Oxidative Coupling/Cyclization for the Construction of 1,4-Dihydropyridine Derivatives.

An efficient copper-catalyzed cascade cyclization reaction for the preparation of polysubstituted 1,4-dihydropyridines between N-arylglycine esters and 1,3-dicarbonyl compounds using molecular oxygen as the terminal oxidant has been described. Various N-arylglycine esters 1 and 1,3-dicarbonyl compounds 2 were able to undergo the cascade reaction smoothly to afford the desired products 3 in satisfactory yields. The cascade reaction has the advantages of good functional group tolerance and mild reaction conditions. A possible mechanism has also been proposed on the basis of control experiments.

Facile synthesis of bis(indolyl)methanes catalyzed by α-chymotrypsin.

A mild and efficient method catalyzed by α-chymotrypsin was developed for the synthesis of bis(indolyl)methanes through a cascade process between indole and aromatic aldehydes. In the ethanol aqueous solution, a green medium, a wide range of aromatic aldehydes could react with indole to afford the desired products with moderate to good yields (from 68% to 95%) using a little α-chymotrypsin as catalyst.