Bifunctional Ligand Enables Gold-Catalyzed Propargyl C-H Functionalization via Reactive Gold Allenylidene Intermediate.

Gold allenylidene species have been seldom exploited as reactive intermediates in synthetically versatile catalytic reactions. By employing alkynylbenziodoxoles as the substrates and bifunctional WangPhos as the metal ligand, this work demonstrated ready catalytic access to these intermediates of general substitution patterns and their electrophilic reactivities at the γ-carbon center with a diverse range of nucleophiles. The reaction is driven by the reductive decomposition of the benziodoxole moiety and achieves the replacement of a propargylic proton with a N/O/C-based nucleophile, hence realizing reactivity umpolung. Corroborated by DFT calculations, the reaction mechanism involves a mild propargylic deprotonation. In contrast to prior works employing a tertiary amine functionality, A barely BrØnsted-basic amide group in WangPhos is surprisingly effective in deprotonation at the propargylic position under a gold-ligand cooperation regime.

Sequential radical and cationic reactivity at separated sites within one molecule in solution.

Distonic radical cations (DRCs) with spatially separated charge and radical sites are expected to show both radical and cationic reactivity at different sites within one molecule. However, such "dual" reactivity has rarely been observed in the condensed phase. Herein we report the isolation of crystalline 1λ2,3λ2-1-phosphonia-3-phosphinyl-cyclohex-4-enes 2a,b˙+, which can be considered delocalized DRCs and were completely characterized by crystallographic, spectroscopic, and computational methods. These DRCs contain a radical and cationic site with seven and six valence electrons, respectively, which are both stabilized via conjugation, yet remain spatially separated. They exhibit reactivity that differs from that of conventional radical cations (CRCs); specifically they show sequential radical and cationic reactivity at separated sites within one molecule in solution.

Laser direct overall water splitting for H2 and H2O2 production.

Hydrogen (H2) and hydrogen peroxide (H2O2) play crucial roles as energy carriers and raw materials for industrial production. However, the current techniques for H2 and H2O2 production rely on complex catalysts and involve multiple intermediate steps. In this study, we present a straightforward, environmentally friendly, and highly efficient laser-induced conversion method for overall water splitting to simultaneously generate H2 and H2O2 at ambient conditions without any catalysts. The laser direct overall water splitting approach achieves an impressive light-to-hydrogen energy conversion efficiency of 2.1%, with H2 production rates of 2.2 mmol/h and H2O2 production rates of 65 µM/h in a limited reaction area (1 mm2) within a short real reaction time (0.36 ms/h). Furthermore, we elucidate the underlying physics and chemistry behind the laser-induced water splitting to produce H2 and H2O2. The laser-induced cavitation bubbles create an optimal microenvironment for water-splitting reactions because of the transient high temperatures (104 K) surpassing the chemical barrier required. Additionally, their rapid cooling rate (1010 K/s) hinders reverse reactions and facilitates H2O2 retention. Finally, upon bubble collapse, H2 is released while H2O2 remains dissolved in the water. Moreover, a preliminary amplification experiment demonstrates the potential industrial applications of this laser chemistry. These findings highlight that laser-based production of H2 and H2O2 from water holds promise as a straightforward, environmentally friendly, and efficient approach on an industrial scale beyond conventional chemical catalysis.

Chalcone-Based Synthesis of Tetrahydropyridazines via Cloke-Wilson-Type Rearrangement-Involved Tandem Reaction between Cyclopropyl Ketones and Hydrazines.

A facile and efficient approach for the synthesis of multisubstituted tetrahydropyridazines starting from cyclopropyl ketones and hydrazines has been developed. The transformation is chalcone-based and takes place via a Cloke-Wilson-type rearrangement-involved tandem reaction catalyzed by TfOH in HFIP.

Efficient and Rapid Hydrogen Extraction from Ammonia-Water via Laser Under Ambient Conditions without Catalyst.

As a good carrier of hydrogen, ammonia-water has been employed to extract hydrogen in many ways. Here, we demonstrate a simple, green, ultrafast, and highly efficient method for hydrogen extraction from ammonia-water by laser bubbling in liquids (LBL) at room temperature and ambient pressure without catalyst. A maximum apparent yield of 33.7 mmol/h and a real yield of 93.6 mol/h were realized in a small operating space, which were far higher than the yields of most hydrogen evolution reactions from ammonia-water under ambient conditions. We also established that laser-induced cavitation bubbles generated a transient high temperature, which enabled a very suitable environment for hydrogen extraction from ammonia-water. The laser used here can serve as a demonstration of potentially solar-pumped catalyst-free hydrogen extraction and other chemical synthesis. We anticipate that the LBL technique will open unprecedented opportunities to produce chemicals.

Manganese-catalyzed Efficient Synthesis of N-heterocycles and Aminoketones Using Glycerol as a C3 Synthon.

Glycerol is one of the important biomass-derived feedstocks and the high-value utilizations of glycerol have attracted much attentions in recent years. Herein, we report a manganese catalyzed dehydrogenative coupling of glycerol with amines for the synthesis of substituted 2-methylquinoxalines, 2-ethylbenzimidazoles, and α-aminoketones without any external oxidant. In these reactions, NHC-based pincer manganese complex featuring a pyridine backbone displayed high catalytic activity and selectivity, in which hydrogen and water were produced as the only by-products using glycerol as a C3 synthon.

Unveiling the Activity and Mechanism Alterations by Pyrene Decoration on a Co(II) Macrocyclic Catalyst for CO2 Reduction.

Mechanistic studies involving characterization of crucial intermediates are desirable for rational optimization of molecular catalysts toward CO2 reduction, while fundamental challenges are associated with such studies. Herein we present the systematic mechanistic investigations on a pyrene-appended CoII macrocyclic catalyst in comparison with its pyrene-free prototype. The comparative results also verify the reasons of the higher catalytic activity of the pyrene-tethered catalyst in noble-metal-free CO2 photoreduction with various photosensitizers, where a remarkable apparent quantum yield of 36±3 % at 425 nm can be obtained for selective CO production. Electrochemical and spectroelectrochemical studies in conjunction with DFT calculations between the two catalysts have characterized the key CO-bound intermediates and revealed their different CO-binding behavior, demonstrating that the pyrene group endows the corresponding CoII catalyst a lower catalytic potential, a higher stability, and a greater ease in CO release, all of which contribute to its better performance.

Enantioselective Multifunctionalization with Rh Carbynoids.

Multifunctionalization from the interception of active intermediates is an attractive synthetic strategy for the efficient construction of complex molecular scaffolds in an atom and step economic fashion. However, the design of reactions involving metal carbynoids that exhibit carbene/carbocation behavior is currently limited, and developing catalyst-controlled highly enantioselective versions poses significant challenges. In this study, we present the first asymmetric trifunctionalization reactions with rhodium carbynoids. This reaction unveils the distinctive reactivity of the carbynoid precursor, enabling it to react with simultaneously two nucleophiles and one electrophile. This process involves the formation of two distinct carbene ylides with the alcohol/carbamate and the trapping of one ylide with the imine, resulting in the formation of three new bonds. Furthermore, this strategy allows for the divergent synthesis of a wide array of ß-amino esters in high yields and exceptional enantioselectivity.

Feature Analysis in High-Dimensional Data: Structure-Activity Relationships of Lewis Acid-Transition-Metal Complex-Catalyzed H2 Activation.

Lewis acid-transition metal (LA-TM) catalysts have been proven to have an advantage in catalyzing hydrogen activation. Herein, a high-dimensional structure-activity relationship study is performed for LA-TM-catalyzed hydrogen activation by density functional theory calculations. The DPB-Ni complex is taken as the representative catalyst, and the explored Lewis acid sites and transition-metal centers include B, Al, Ga and Ni, Pd, Pt, respectively. Totally, four general hydrogen activation mechanisms are systematically studied among the nine catalytic systems. The Ga-Ni system undergoes the lowest free energy of activation (11.0 kcal/mol), which is considered to be the optimal combination of the Lewis acid site and transition-metal center. Furthermore, more than 100 parameters are used to analyze the structure-activity relationship, including the physical structure, the bond order, the atom charge, and many other properties. Key parameters of important structures are dug out to show a high correlation with the activity of the LA-TM systems, including the M-H2 distance, the H-H bond length, the second-order perturbation stabilization energy of M-H2, the bond order of the LA-TM, and so on. The multivariable analysis indicates that the feature related to the basic elemental properties and the global feature codetermine the activity of the catalyst. In the LA-TM system, the combination of IpLA/IpTM (Ip, the first ionization energy, the feature related to basic elemental properties) and the chemical hardness (the global feature) can better explain the activity of the catalyst. The IpLA/IpTM reflects the difficulty of breaking the LA-TM bond, affecting the reaction site of activating hydrogen. The hardness reflects the stability and reactivity of LA-TM-RC complexes. The above two features with the addition of the LA-TM bond length (the local feature) can better reflect the activity of the LA-TM system-catalyzed H2 activation. The feature combinations and the method of multidimensional data analysis should be informative guidance for the rational design of efficient LA-TM catalysts for H2 activation.

Laser-Induced Methanol Decomposition for Ultrafast Hydrogen Production.

Methanol (CH3OH) is a liquid hydrogen (H2) source that effectively releases H2 and is convenient for transportation. Traditional thermocatalytic CH3OH reforming reaction is used to produce H2, but this process needs to undergo high reaction temperature (e.g., 200 °C) along with a catalyst and a large amount of carbon dioxide (CO2) emission. Although photocatalysis and photothermal catalysis under mild conditions are proposed to replace the traditional thermal catalysis to produce H2 from CH3OH, they still inevitably produce CO2 emissions that are detrimental to carbon neutrality. Here, we, for the first time, report an ultrafast and highly selective production of H2 without any catalysts and no CO2 emission from CH3OH by laser bubbling in liquid (LBL) at room temperature and atmospheric pressure. We demonstrate that a super high H2 yield rate of 33.41 mmol·h-1 with 94.26% selectivity is achieved upon the laser-driven process. This yield is 3 orders of magnitude higher than the best value reported for photocatalytic and photothermal catalytic H2 production from CH3OH to date. The energy conversion efficiency of laser light to H2 and CO can be up to 8.5%. We also establish that the far from thermodynamic equilibrium state with high temperature inside the laser-induced bubble and the kinetic process of rapid quenching of bubbles play crucial roles in H2 production upon LBL. Thermodynamically, the high temperature induced using laser in bubbles ensures fast and efficient release of H2 from CH3OH decomposition. Kinetically, rapidly quenching of laser-induced bubbles can inhibit reverse reaction and can keep the products in the initial stage, which guarantees high selectivity. This study presents a laser-driven ultrafast and highly selective production of H2 from CH3OH under normal conditions beyond catalytic chemistry.

Mn(I)-catalyzed sigmatropic rearrangement of ß, γ-unsaturated alcohols.

Sigmatropic rearrangement provides a versatile strategy to site-selectively reorganize carbon-skeleton with high atom- and step-economy. Herein, we disclose a Mn(I)-catalyzed sigmatropic rearrangement of ß, γ-unsaturated alcohols via C-C σ bond activation. A variety of α-aryl-allylic alcohols and α-aryl-propargyl alcohols could undergo in-situ 1,2- or 1,3- sigmatropic rearrangements to allow for converting to complex structural arylethyl- and arylvinyl- carbonyl compounds under a simple catalytic system. More importantly, this catalysis model can be further applied to assemble macrocyclic ketones through bimolecular [2n + 4] coupling-cyclization and monomolecular [n + 1] ring-extension. The presented skeleton rearrangement would be a useful tool complementary to the traditional molecular rearrangement.

Updated Progress of the Copper-Catalyzed Borylative Functionalization of Unsaturated Molecules.

Borylation has become a powerful method to synthesize organoboranes as versatile building blocks in organic synthesis, medicinal chemistry, and materials science. Copper-promoted borylation reactions are extremely attractive due to the low cost and non-toxicity of the copper catalyst, mild reaction conditions, good functional group tolerance, and convenience in chiral induction. In this review, we mainly updated recent advances (from 2020 to 2022) in the synthetic transformations in C=C/C≡C multiple bonds, and C=E multiple bonds mediated by copper boryl systems.

Reactivities of α-Oxo BMIDA Gold Carbenes Generated by Gold-Catalyzed Oxidation of BMIDA-Terminated Alkynes.

An oxidative strategy is reported to access α-oxo BMIDA gold carbenes directly from BMIDA-terminated alkynes. Besides offering expedient access to seldom studied boryl metal carbenes, these BMIDA gold carbene species undergo facile insertions into methyl, methylene, methine, and benzylic C-H bonds in the absence of the Thorpe-Ingold effect. They also undergo efficient OH insertion, cyclopropanation, and F-C alkylations. This chemistry provides rapid access to structurally diverse α-BMIDA ketones, which are scarcely documented. In combination with DFT studies, the role of BMIDA is established to be an electron-donating group that attenuates the high electrophilicity of the gold carbene center.

Synthesis of Chiral Sulfoximines via Iridium-Catalyzed Regio- and Enantioselective C-H Borylation: A Remarkable Sidearm Effect of Ligand.

Transition metal-catalyzed enantioselective C-H activation of prochiral sulfoximines for non-annulated products remains a formidable challenge. We herein report iridium-catalyzed enantioselective C-H borylation of N-silyl diaryl sulfoximines using a well-designed chiral bidentate boryl ligand with a bulky side arm. This method is capable of accommodating a broad range of substrates under mild reaction conditions, affording a vast array of chiral sulfoximines with high enantioselectivities. We also demonstrated the synthetic utility on a preparative-scale C-H borylation for diverse downstream transformations, including the synthesis of chiral version of bioactive molecules. Computational studies showed that the bulky side arm of the ligand confers high regio- and enantioselectivity through steric effect.

Palladium-Catalyzed Cascade Cyclization for the Synthesis of Fused Benzo-Aza-Oxa-[5-6-5] Tetracycles.

A novel and expedient cascade strategy has been demonstrated for the synthesis of fused benzo-aza-oxa-[5-6-5] tetracycles in high yields and diastereoselectivities (up to 20 : 1 dr). The strategy was fulfilled through palladium-catalyzed oxidative convergent assembly of functionally divergent anilines and 3-butenoic acid with five chemical bonds constructed. Coupled with control experiments and deuterium labelled studies, DFT calculations were performed for the proposed mechanism. The utility of the illustrated strategy is emphasized by gram-scale syntheses, late-stage functionalization, and the transformation to a key core of natural products such as martinellic acid and seneciobipyrrolidine.

Palladium-catalysed selective oxidative amination of olefins with Lewis basic amines.

Amines are prominent in natural products, pharmaceutical agents and agrochemicals. Moreover, they are synthetically valuable building blocks for the construction of complex organic molecules and functional materials. However, amines, especially aliphatic and aromatic amines with free N-H bonds, tend to coordinate with transition metals and deactivate the catalyst, posing a tremendous challenge to applying Lewis basic amines in the amination of olefins. Here we present an example of oxidative amination of simple olefins with various Lewis basic amines. The combination of a palladium catalyst, 2,6-dimethyl-1,4-benzoquinone and a phosphorous ligand leads to the efficient synthesis of alkyl and aryl allylamines. A series of allylamines were obtained with good yields and excellent regio- and stereoselectivities. Intramolecular amination to synthesize tetrahydropyrrole and piperidine derivatives was also realized. Mechanistic investigations reveal that the reaction undergoes allylic C(sp3)-H activation and subsequent functionalization.

Dual electronic effects achieving a high-performance Ni(II) pincer catalyst for CO2 photoreduction in a noble-metal-free system.

A carbazolide-bis(NHC) NiII catalyst (1; NHC, N-heterocyclic carbene) for selective CO2 photoreduction was designed herein by a one-stone-two-birds strategy. The extended π-conjugation and the strong σ/π electron-donation characteristics (two birds) of the carbazolide fragment (one stone) lead to significantly enhanced activity for photoreduction of CO2 to CO. The turnover number (TON) and turnover frequency (TOF) of 1 were ninefold and eightfold higher than those of the reported pyridinol-bis(NHC) NiII complex at the same catalyst concentration using an identical Ir photosensitizer, respectively, with a selectivity of ∼100%. More importantly, an organic dye was applied to displace the Ir photosensitizer to develop a noble-metal-free photocatalytic system, which maintained excellent performance and obtained an outstanding quantum yield of 11.2%. Detailed investigations combining experimental and computational studies revealed the catalytic mechanism, which highlights the potential of the one-stone-two-birds effect.

Solution structure of a thrombin binding aptamer complex with a non-planar platinum(ii) compound.

Thrombin Binding Aptamer (TBA) is a monomolecular well-defined two G-tetrad antiparallel G-quadruplex DNA that inhibits the activity of human α-thrombin. In this report, we synthesized a quasi-cross-shaped platinum(ii) compound (L'2LPt) with one cyclometalated and two carbene ligands. We found L'2LPt has selective affinity to bind the TBA G-quadruplex. A fibrinogen clotting assay revealed that L'2LPt can abrogate the inhibitory activity of TBA against thrombin. We solved the 1 : 1 L'2LPt-TBA complex structure by NMR, which revealed a unique self-adaptive property of L'2LPt upon binding to TBA. In the complex, a carbene ligand of L'2LPt rotates to pair with the cyclometalated ligand to form a plane stacking over half of the TBA G-tetrad and covered by lateral TT loops. It is notable that the heavy atom Pt stays out of the G-tetrad. Meanwhile, the other carbene ligand remains relatively perpendicular and forms a hydrogen bond with a guanine to anchor the L'2LPt position. This structure exhibits a quasi-cross-shaped Pt(ii) compound bound to the G-quadruplex with an unusual "wall-mounted" binding mode. Our structures provide insights into the specific recognition of antiparallel G-quadruplex DNA by a self-adaptive Pt(ii) compound and useful information for the design of selective G-quadruplex targeting non-planar molecules.

Co-facial π-π Interaction Expedites Sensitizer-to-Catalyst Electron Transfer for High-Performance CO2 Photoreduction.

The sunlight-driven reduction of CO2 into carbonaceous fuels can lower the atmospheric CO2 concentration and provide renewable energy simultaneously, attracting scientists to design photocatalytic systems for facilitating this process. Significant progress has been made in designing high-performance photosensitizers and catalysts in this regard, and further improvement can be realized by installing additional interactions between the abovementioned two components, however, the design strategies and mechanistic investigations on such interactions remain challenging. Here, we present the construction of molecular models for intermolecular π-π interactions between the photosensitizer and the catalyst, via the introduction of pyrene groups into both molecular components. The presence, types, and strengths of diverse π-π interactions, as well as their roles in the photocatalytic mechanism, have been examined by 1H NMR titration, fluorescence quenching measurements, transient absorption spectroscopy, and quantum chemical simulations. We have also explored the rare dual emission behavior of the pyrene-appended iridium photosensitizer, of which the excited state can deliver the photo-excited electron to the pyrene-decorated cobalt catalyst at a fast rate of 2.60 × 106 s-1 via co-facial π-π interaction, enabling a remarkable apparent quantum efficiency of 14.3 ± 0.8% at 425 nm and a high selectivity of 98% for the photocatalytic CO2-to-CO conversion. This research demonstrates non-covalent interaction construction as an effective strategy to achieve rapid CO2 photoreduction besides a conventional photosensitizer/catalyst design.

A Stable and Conductive Covalent Organic Framework with Isolated Active Sites for Highly Selective Electroreduction of Carbon Dioxide to Acetate.

Electroreduction of CO2 to acetate provides a promising strategy to reduce CO2 emissions and store renewable energy, but acetate is usually a by-product. Here, we show a stable and conductive two-dimensional phthalocyanine-based covalent-organic framework (COF) as an electrocatalyst for reduction of CO2 to acetate with a single-product Faradaic efficiency (FE) of 90.3(2)% at -0.8 V (vs. RHE) and a current density of 12.5 mA cm-2 in 0.1 M KHCO3 solution. No obvious degradation was observed over 80 hours of continuous operation. Combined with the comparison of the properties of other catalysts with isolated metal active sites, theoretical calculations and in situ infrared spectroscopy revealed that the isolated copper-phthalocyanine active site with high electron density is conducive to the key step of C-C coupling of *CH3 with CO2 to produce acetate, and can avoid the coupling of *CO with *CO or *CHO to produce ethylene and ethanol.