可见光光催化:缺电子杂环、苯环与芳基偶氮盐的直接芳基化偶联反应

发展了可见光照射下Ru(bpy)₃(PF₆)₂催化缺电子杂环C-H活化与芳基偶氮盐的交叉偶联反应.在室温、可见光照射下,各种缺电子杂环与芳基偶氮盐发生高效的偶联反应,同时在相似的条件下,普通苯环也能有效地与芳基偶氮盐偶联形成新C-C键化合物.     

The Keto-Switched Photocatalysis of Reconstructed Covalent Organic Frameworks for Efficient Hydrogen Evolution

The keto-switched photocatalysis of covalent organic frameworks (COFs) for efficient H₂ evolution was reported for the first time by engineering, at a molecular level, the local structure and component of the skeletal building blocks. A series of imine-linked BT-COFs were synthesized by the Schiff-base reaction of 1, 3, 5-benzenetrialdehyde with diamines to demonstrate the structural reconstruction of enol to keto configurations by alkaline catalysis. The keto groups of the skeletal building blocks served as active injectors, where hot π-electrons were provided to Pt nanoparticles (NPs) across a polyvinylpyrrolidone (PVP) insulting layer. The characterization results, together with density functional theory calculations, indicated clearly that the formation of keto-injectors not only made the conduction band level more negative, but also led to an inhomogeneous charge distribution in the donor-acceptor molecular building blocks to form a strong intramolecular built-in electric field. As a result, visible-light photocatalysis of TP-COFs-1 with one keto group in the skeletal building blocks was successfully enabled and achieved an impressive H₂ evolution rate as high as 0.96 mmol g⁻¹ h⁻¹. Also, the photocatalytic H₂ evolution rates of the reconstructed BT-COFs-2 and -3 with two and three keto-injectors were significantly enhanced by alkaline post-treatment.     

Dimethyl Carbonate as a Sacrificial Molecule for the Synthesis of 5‐Memebered N‐ and O‐Heterocycles

In the last twenty years DMC has been employed as an efficient methylating and methoxycarbonylating agent with several monodentate and bidentate nucleophiles, showing great selectivity and unexpected results. In this short review we report on yet another application of DMC chemistry i.e. the synthesis of 5‐membered N‐ and O‐heterocycles. In these reactions DMC acts as a sacrificial molecule since it is not present in the final products, but only in the reaction intermediates as an halogen‐free leaving group. This DMC‐based synthesis of heterocycles resulted of general application, as it is effective for aliphatic and aromatic 1,4‐diols, incorporating several functionalities (primary, secondary, tertiary, allylic, phenolic), as well as, for bifunctional compounds i.e. 4‐amino‐1‐butanol. This synthetic procedure was also employed for industrially relevant compounds such as (‐)‐norlabdane oxide and isosorbide showing to maintain the chiral integrity of the substrate. In one case intramolecular cyclisation of isosorbide was also observed to achieve a strained tricyclic derivative. Comparing this reaction methodology with a chlorine based procedure, the DMC‐mediated pathway is quantitative, occurs in one step, does not require any chlorine‐based chemical or strong acid and does not produce any chlorinated waste material.     

Role of Microwaves in the Synthesis of Fused Five-Membered Heterocycles with Three N-Heteroatoms

The development of new strategies for the synthesis of small-sized heterocycles has remained a highly attractive but challenging proposition. An overview of the application of microwave irradiation in three nitrogen atoms containing fused five-membered heterocyclic compounds synthesis is presented, focusing on the developments in the past 5–10 years. This contribution covers the literature concerning the total synthesis of N,N,N-heterocycles. The literature data are summarized based on the type of cycles.     

Trifluoromethylation of non-activated aldimines with trimethyl(trifluoromethyl)silane in the presence of tetramethylammonium fluoride: A closer look into the reaction route

The reactions of non-activated aldimines with trimethyl(trifluoromethyl)silane and 1 equiv. of tetramethylammonium fluoride proceed via the formation of tetramethylammonium amides which were identified by low-temperature ¹⁹F NMR experiments. Consecutive reactions of the salts formed in situ with electrophiles yielded trifluoromethylated amines. Fluoride elimination is observed in the absence of electrophilic substrates leading to the formation of difluoromethylated ketimines.     

Hydrogenation and Ammoniation of SrTiO3 for an Enhanced Visible-light Photocatalysis

Hydrogenation and ammoniation of SrTiO₃ (STO), a normal ultraviolet photocatalyst, were performed by annealing STO〈100〉in H₂:N₂=5%:95% and NH₃, respectively, at various tem-peratures T. It was found that hydrogenation at T≥900 oC remarkably enhanced the UV photocatalytic ability of STO, but the visible-light photocatalysis was still unavailable, while ammoniation at T≥800 oC introduced the N doping, resulting in visible-light photocat-alytic activity. Furthermore, when a hydrogenated STO was subjected to ammoniation, the visible-light photocatalytic ability was nearly the same as that of the ammoniated one; but the hydrogenation of an ammoniated one significantly enhanced visible-light photocatalysis, indicating a synergetic effect of hydrogenation and ammoniation. Discussions and identifi-cations have been made to analyze these results.     

Silica Gel,an Effective Catalyst for the Reaction of Electron-Deficient Nitro-Olefins with Nitrogen Heterocycles

The reaction of electron-deficient olefins with nitrogen heterocycles such as pyrrole and indole was examined in the presence of silica gel at room temperature under stirring at solvent-free conditions. It was found that silica gel is an effective catalyst for this conjugate addition. This work resulted in the formation of monosubstituted pyrroles selectively as a major product except in a few cases where disubstituted pyrroles were also formed as side products. Thus, a simple, rapid, efficient, environmentally benign, and solvent-free method was established.     

Fixation of Atmospheric Nitrogen: Synthesis of Heterocycles with Atmospheric Nitrogen as the Nitrogen Source

Dry air is the source of molecular nitrogen for reactions with TiL₄, Li, and TMSCl (L = Cl, OiPr; TMS = trimethylsilyl). The nitrogen–titanium complexes thus prepared can be used to synthesize indoles, pyrroles, and lactams from carbonyl compounds. Applying this method to 1 provides access to 2 , the key compound in the synthesis of (±)-lycopodine.     

A Simple Iridicycle Catalyst for Efficient Transfer Hydrogenation of N‐Heterocycles in Water

A cyclometalated iridium complex is shown to catalyse the transfer hydrogenation of various nitrogen heterocycles, including but not limited to quinolines, isoquinolines, indoles and pyridinium salts, in an aqueous solution of HCO₂H/HCO₂Na under mild conditions. The catalyst shows excellent functional‐group compatibility and high turnover number (up to 7500), with catalyst loadings as low as 0.01 mol % being feasible. Mechanistic investigation of the quinoline reduction suggests that the transfer hydrogenation proceeds via both 1,2‐ and 1,4‐addition pathways, with the catalytic turnover being limited by the step of hydride transfer.     

Novel Procedure for the Coupling of Sterically Hindered Electron-Deficient Anilines to the 6-Position of the Purine Core

Sterically hindered electron-deficient anilines are coupled to the 6-position of the purine core only when activated as their corresponding TFA-amide. The free anilines did not react under all conditions tested. After aqueous work-up, the TFA-group is lost.

This procedure provides a new tool in the construction of purines functionalized with a sterically hindered electron-deficient aniline in the 6-position.      

Direct Arylation of N‐Heteroarenes with Aryldiazonium Salts by Photoredox Catalysis in Water

A highly effective visible light‐promoted “radical‐type” coupling of N‐heteroarenes with aryldiazonium salts in water has been developed. The reaction proceeds at room temperature with [Ru(bpy)₃]Cl₂ ? 6 H₂O as a photosensitizer and a commercial household light bulb as a light source. Pyridine and a variety of substituted pyridines are effective substrates under these reaction conditions, and only monosubstituted products are formed with different regioselectivities. Using aqueous formic acid as solvent, an array of xanthenes, thiazole, pyrazine, and pyridazine are compatible with this new arylation approach. The broad substrate scope, mild reaction conditions, and use of water as reaction solvent make this procedure a practical and environmentally friendly method for the synthesis of compounds containing aryl‐heteroaryl motifs.     

NaCl as a Novel and Green Catalyst for the Synthesis of Biodynamic Spiro Heterocycles in Water Under Sonication

An efficient and novel green catalytic protocol for the synthesis of biologically important spirooxindole derivatives is developed in a one-pot, three-component approach involving substituted isatin, activated methylene reagent, and 3-methyl-1-phenyl-2-pyrazolin-5-one in water under sonication. This report describes the use of sodium chloride as a nonacidic and green catalyst for a variety of substrates. The advantageous features of this methodology are the environmentally benign character, operational simplicity, high yield processing, easy handling, and the fact that the products do not need to be purified.

Direct Photocatalysis for Organic Synthesis by Using Plasmonic‐Metal Nanoparticles Irradiated with Visible Light

Recent advances in direct‐use plasmonic‐metal nanoparticles (NPs) as photocatalysts to drive organic synthesis reactions under visible‐light irradiation have attracted great interest. Plasmonic‐metal NPs are characterized by their strong interaction with visible light through excitation of the localized surface plasmon resonance (LSPR). Herein, we review recent developments in direct photocatalysis using plasmonic‐metal NPs and their applications. We focus on the role played by the LSPR of the metal NPs in catalyzing organic transformations and, more broadly, the role that light irradiation plays in catalyzing the reactions. Through this, the reaction mechanisms that these light‐excited energetic electrons promote will be highlighted. This review will be of particular interest to researchers who are designing and fabricating new plasmonic‐metal NP photocatalysts by identifying important reaction mechanisms that occur through light irradiation.     

Recyclable alkylated fac-Ir(ppy)3 complex as a visible-light photoredox catalyst for the synthesis of 3-trifluoromethylated and 3-difluoroacetylated coumarins

A recyclable fac-tris(heptadecanyl-2-phenylpyridine) iridium [fac-Ir(hdppy)₃] photocatalyst was synthesized. The hexane-phase-selective solubility of fac-Ir(hdppy)₃ in a thermomorphic multicomponent solvent (TMS) allowed its easy recycling by automatic liquid/liquid separation at room temperature. The excellent catalytic and recoverable activities of fac-Ir(hdppy)₃ were demonstrated via trifuoromethylation and difluoroacetylation reactions of phenyl 3-phenylpropiolate under visible-light irradiation in a TMS system.     

Multicomponent Reactions for the Synthesis of Heterocycles

Multicomponent domino reactions (MDRs) serve as a rapid and efficient tool for the synthesis of versatile heterocycles, particularly those containing structural diversity and complexity, by a one‐pot operation. These reactions can dramatically reduce the generation of chemical wastes, costs of starting materials, and the use of energy and manpower. Moreover, the reaction period can be substantially shortened. This Review covers recent advances on multicomponent domino reactions for the construction of five‐, six‐, and seven‐membered heterocyclic skeletons and their multicyclic derivatives.     

The first example of a “click” reaction with a carboranyl azide and an olefin

While typical organic azides have long been known to undergo 1–3 dipolar cycloadditions with strained CC multiple bonds, such chemistry has never been reported between organomimetic carboranyl azides and alkenes. Here we show that the carborane o-PhCN₃CB₁₀H₁₀ readily undergoes cycloaddition with norbornene at ambient temperature to afford the corresponding triazole adduct with perfect exo-selectivity. The structure of the ensuing heterocycle was unambiguously determined by multinuclear NMR, correlation NMR, and single crystal X-ray diffraction experiments. This first example of such reactivity demonstrates a method to easily introduce carborane clusters directly to scaffolds of interest, without having an organic spacer between the azide functionality and cluster.     

Microtubing‐Reactor‐Assisted Aliphatic C−H Functionalization with HCl as a Hydrogen‐Atom‐Transfer Catalyst Precursor in Conjunction with an Organic Photoredox Catalyst

Chlorine radical, which is classically generated by the homolysis of Cl₂ under UV irradiation, can abstract a hydrogen atom from an unactivated C(sp³)?H bond. We herein demonstrate the use of HCl as an effective hydrogen‐atom‐transfer catalyst precursor activated by an organic acridinium photoredox catalyst under visible‐light irradiation for C?H alkylation and allylation. The key to success relied on the utilization of microtubing reactors to maintain the volatile HCl catalyst. This photomediated chlorine‐based C?H activation protocol is effective for a variety of unactivated C(sp³)?H bond patterns, even with primary C(sp³)?H bonds, as in ethane. The merit of this strategy is illustrated by rapid access to several pharmaceutical drugs from abundant unfunctionalized alkane feedstocks.     

Ring Enlargement of Three‐Membered Boron Heterocycles upon Reaction with Organic π Systems: Implications for the Trapping of Borylenes

New low‐energy pathways for the reaction between substituted boriranes and borirenes with unsaturated hydrocarbons (ethyne or ethene) were discovered using density functional and coupled cluster theory. The interaction between the π bond of the hydrocarbon and the empty p orbital of the boron center leads to ring expansion of the three‐membered to a five‐membered boron heterocycle. The reactions are strongly exothermic and have low or even no barriers. They involve intermediates with a pentacoordinate boron center with two hydrocarbon molecules coordinating to boron akin to metal‐olefin complexes. These borylene complexes are shallow minima on the potential energy surfaces. But significantly higher barriers for ring formation are computed for 1,5‐cyclooctadiene and dibenzocyclooctatetraene complexes of borylenes, making these complexes likely detectable under appropriate experimental conditions. Our computational findings have implications for the interpretation of trapping experiments of thermally generated small borylenes with excess of small π systems. Because of very low barriers for reactions of three‐membered boron heterocycles with π systems and the at least locally large excess of the latter under such conditions, formation of five‐membered boron heterocycles should be considered.     

Surface-functionalized Carbon Black as Catalyst for the Direct Production of Hydrogen Peroxide by the Oxidation of Hydroxylamine

Carbon black (CB) without micropores was functionalized by mixed acid and used to explore the surface chemistry effect on the production of hydrogen peroxide (H₂O₂). The CB materials were characterized by N₂ adsorption‐desorption, XRD, SEM, FTIR, and TPD. The results of different characterization methods indicated that both the textural features and the surface chemical properties of CB were significantly modified by the acidic treatment. The catalytic performance of the modified CBs for hydroxylamine (NH₂OH) oxidation increased with increasing the surface oxygen‐containing species. The yield of H₂O₂ approached 30% with the corresponding concentration of 73.9 mmol·L^?1 (w=0.25%) over the most promising CB catalyst, which was much superior to the results obtained on supported noble metals. Correlations between catalytic activity and concentration of different surface functional groups on the CB samples confirmed that the quinonoid species might be the active species.