Reaction Mechanism Research Articles

Enabling high throughput deep reinforcement learning with first principles to investigate catalytic reaction mechanisms

Exploring catalytic reaction mechanisms is crucial for understanding chemical processes, optimizing reaction conditions, and developing more effective catalysts. We present a reaction-agnostic framework based on high-throughput deep reinforcement learning with first principles (HDRL-FP) that offers excellent generalizability for investigating catalytic reactions. HDRL-FP introduces a generalizable reinforcement learning representation of catalytic reactions constructed solely from atomic positions, which are subsequently mapped to first-principles-derived potential energy landscapes. By leveraging thousands of simultaneous simulations on a single GPU, HDRL-FP enables rapid convergence to the optimal reaction path at a low cost. Its effectiveness is demonstrated through the studies of hydrogen and nitrogen migration in Haber-Bosch ammonia synthesis on the Fe(111) surface. Our findings reveal that the Langmuir-Hinshelwood mechanism shares the same transition state as the Eley-Rideal mechanism for H migration to NH2, forming ammonia. Furthermore, the reaction path identified herein exhibits a lower energy barrier compared to that through nudged elastic band calculation.

Theoretical study of the reaction of organic peroxyl radicals with alkenes and their accretion products involved in the atmospheric nucleation

Organic peroxy radicals, including alkyl peroxy radicals (RO2) and acyl peroxy radicals (RC(O)O2), are crucial intermediates in the atmospheric photochemical reactions of volatile organic compounds and directly or indirectly affect the distribution of other species (e.g., HO2 radicals, NOx, OH radicals, and alkenes). However, the atmospheric reactions of organic peroxyl radicals with alkenes (RO2 + alkene reactions) are not fully understood. The present study used theoretical calculations to investigate the reaction mechanisms of various organic peroxy radicals with different alkenes, with the aim of clarifying the influence of molecular structure on RO2 + alkene and RC(O)O2 + alkene reactions. Furthermore, we investigated the nucleation mechanisms of the subsequent oxidation products. The results show that the reaction rate constants for RC(O)O2 + alkene reactions are 1–6 orders of magnitude higher than those for RO2 + alkene reactions. The addition products formed by organic peroxy radicals with alkenes not only undergo monomolecular reactions to generate epoxides, but also participate in O2 addition to yield the accretion products ROOR’. H2SO4 molecules synergistically interact with low-volatility ROOR’ to grow clusters up to the 1–2 nm scale, and the ROOR’ molecules can form pure organic clusters larger than 1 nm, even in the absence of H2SO4 molecules. Our study provides a new perspective on the formation of accretion products in the atmosphere and their involvement in new particle formation.

An experimental and mechanism study on the pyrolysis of sulfur mustard

Experimental studies on the pyrolysis of sulfur mustard (HD) were conducted from 673 to 1473 K using Py-GC/MS combined with two separate columns. The HD pyrolysis rate exceeded 99 % at a pyrolysis time of approximately 2 seconds above 1073 K. The pyrolysis products of HD mainly include ethylene, vinyl chloride, carbon disulfide, thiophene, hydrogen chloride and hydrogen sulfide. The main reaction mechanism of HD pyrolysis was investigated using quantum chemistry methods combined with the TST/VTST theory. At 673 K, the initial reaction pathway of HD primarily involves an intramolecular HCl elimination and the cleavage of the C-S bond. The radical reactions will dominate the pyrolysis of HD once radical pool is formed. The reaction pathways of the important radical intermediates were analyzed, and the formation mechanisms of the main pyrolysis products were investigated. Theoretically, the high-pressure limit rate constants for the major reactions were calculated. This study contributes to a deeper understanding of the HD pyrolysis mechanism and provides a theoretical and data foundation for the destruction of HD.

High valent manganese-oxo species activation of peroxymonosulfate by different phases manganese oxides nanoplates for catalytic water decontamination

Advanced oxidation processes involving high-valent metal-oxo species have garnered increasing attention for their effective pollutant degradation in water. However, less is known about the mechanism of the species in the manganese oxides (MnOx) system. Therefore, it is crucial to design MnOx catalysts to systematically clarify the high-valent metal-oxo species reaction mechanism. In this study, MnOx nanoplates including Mn3O4, Mn5O8, and Mn2O3 were synthesized via a facile thermal treatment of a Mn(OH)2 precursor to activate peroxymonosulfate (PMS) for mechanism studies. The Mn3O4 catalyst exhibited superior catalytic performance and reusability owing to its unique spinel structure and rapid electron transfer properties. The first-order rate constant for Mn3O4 is 0.64 min−1, which is 3.7 and 1.5 times higher than those of Mn5O8 and Mn2O3, respectively. Scavenging experiments, electron paramagnetic resonance, and electrochemical analysis revealed that free radicals played a negligible role, while the formation of high-valent Mn-oxo species was promoted, facilitated by the Mn3O4-PMS* complex. These high-valent Mn-oxo species were highly reactive towards various pollutants. Moreover, the degradation intermediates of bisphenol A (BPA) in the Mn3O4/PMS system were identified, further elucidating the interactions between high-valent Mn-oxo species and BPA. Additionally, the Mn3O4 catalyst exhibited excellent catalytic performance under practical conditions and maintained superior stability over six cycles. This work provides crucial insights into the role of transition metal oxides in activating PMS for the catalytic degradation of emerging pollutants.

Enhanced degradation of sulfathiazole by ionizing radiation activated persulfate and periodate: Performances and mechanisms

Ionizing radiation has attracted significant interests in water purifying. However, it suffers from poor mineralization performance during the decontamination of organic micropollutants such as antibiotics. Herein, the radiolytic degradation of sulfathiazole (STZ) by gamma radiation was investigated. STZ could be completely degraded at 2.0 kGy absorbed dose but TOC removal efficiency was only 22.62 %. Quenching experiments demonstrated that •OH was the main reactive species. Toxicity assessment and phytotoxicity experiments indicated that gamma radiation can comprehensively decrease the toxicity of STZ. Significant enhancements of degradation and mineralization were observed in gamma/persulfate (Gamma/PS) and gamma/periodate (Gamma/PI) processes. The rate constant (k) increased by 1.08 times and TOC removal efficiency increased by 2.01 times with PS addition (1 mM). The k value enhanced by 4.05 times and TOC removal ratio enhanced by 2.66 times with the presence of PI (1 mM). Mechanistic investigation indicated that 1O2 played a major role in STZ degradation in the Gamma/PS and Gamma/PI systems. PI was almost completely transferred into the nontoxic iodate (IO3-), and no toxic reactive iodine species were produced in the Gamma/PI process. Moreover, Gamma/PS and Gamma/PI systems showed a broad-spectrum ability to remove a series of antibiotics. The removal performances and the costs of these systems were competitive compared with other advanced oxidation processes for antibiotics elimination. This study supplied an efficient and sustainable choice for the degradation of antibiotics, and clarified the intrinsic reaction mechanisms in the ionizing radiation-activated PS and PI systems.

Green synthesis of nanostructured 1T/2H-MoS2 hybrid phase with polyol solvents and microwave heating

Green synthesis approaches have attracted greatly of attention in recent years since they address the issues associated with sustainability than conventional synthesis methods. New research fields in green nanoscience are being developed as a result of the incorporation of green chemistry principles into nanoscience. In this paper, the successful microwave-assisted green synthesis of MoS2 nanoparticles in a single pot using polyol solvents such as ethylene glycol and glycerol is demonstrated. The coexistence of 1T and 2H phases in MoS2 nanomaterials was determined using advanced techniques such as XRD, Raman, XPS, and TEM images. The highest 1T proportion obtained was 84.5% when compared to the 2H phase. The reaction mechanism and the phase transition between 1T and 2H were described and illustrated. The role of polyol solvents in the practical synthesis of nano MoS2 under microwave heating is also evaluated and explained. Due to the ability of the metallic 1T phase to enhance electrical conductivity, it is believed that hybrid nanostructures exhibit superior electrochemical performance for energy storage and conversion applications.

Modulation strategies of electrocatalysts for 5-hydroxymethylfurfural oxidation-assisted water splitting

To address energy shortages and environmental issues, prioritizing renewable energy development and usage is crucial. Employing renewable sources for water electrolysis offers a sustainable method for hydrogen generation. Reducing the water electrolysis potential is vital for efficient clean energy conversion and storage. Substituting the anodic oxygen evolution reaction in conventional hydrogen production from water electrolysis with the more thermodynamically favorable 5-hydroxymethylfurfural (HMF) oxidation reaction can greatly decrease overpotential and yield the valuable product 2,5-furan dicarboxylic acid. The key to this process is developing effective electrocatalysts to minimize the potential of the HMF electrooxidation-hydrogen production system. Therefore, this review provides a comprehensive introduction to the modulation strategies that affect the electronic and geometric structure of electrocatalysts for HMF oxidation-assisted water splitting. The strategies encompass heteroatom doping, defect projection, interface engineering, structural design, and multi-metal synergies. The catalysts are assessed from various angles, encompassing structural characterization, reaction mechanisms, and electrochemical performance. Finally, current challenges in the catalyst design and potential development of this promising field are proposed.

Synthesis and characterization of Co(II) porphyrin complex supported on chitosan/graphene oxide nanocomposite for efficient green oxidation and removal of Acid Orange 7 dye

Catalytic degradation of Acid Orange 7 (AO7) by hydrogen peroxide in an aqueous solution has been investigated using cobalt(II) complex of 5, 10, 15, 20 Tetrakis [4-(hydroxy)phenyl] porphyrin [Co(II) TPHPP] covalently supported chitosan/Graphene Oxide nanocomposite [Co(II) TPHPP]-Cs/GO, as highly efficient and recoverable heterogeneous catalyst. The structures and properties of [Co(II) TPHPP]-Cs/GO nanocomposite were characterized by techniques such as UV–Vis, FT-IR, SEM, EDX, TEM, and XRD. The oxidation reaction was followed by recording the UV–Vis spectra of the reaction mixture with time at λmax = 485 nm. [Co(II) TPHPP]-Cs/GO nanocomposite demonstrated high catalytic activity and could decompose 94% of AO7 within 60 min. The factors that may influence the oxidation of Acid Orange 7, such as the effect of reaction temperature, pH, concentration of catalyst, Acid Orange 7, and hydrogen peroxide, have been studied. The results of total organic carbon analysis (TOC) showed 50% of dye mineralization under mild reaction conditions of AO7 (1.42 × 10−4M) with H2O2 (8 × 10−2M) in the presence of [Co(II) TPHPP]-Cs/GO nanocomposite (15 × 10−3 g/ml) and pH = 9 at 40 °C. The reuse and stability of the nanocomposite were examined and remarkably, even after six cycles of reuse, there was no significant degradation or deactivation of the recycled catalyst. Residual organic compounds in the reaction mixture were identified by using GC–MS analyses. The radical scavenging measurements and photoluminescence probing technology of disodium salt of terephthalic acid indicated the formation of the hydroxyl radical as the reactive oxygen species in the [Co(II) TPHPP]-Cs/GO nanocomposite/H2O2 system. A mechanism for the oxidation reaction has been discussed.

Copper-based nanoparticles supported on functionalized kaolinite for catalytic reduction of nitroaromatic compounds

A catalyst was synthesized by in situ reduction of Cu(II) ions on kaolinite particles. The clay mineral was modified by grafting propane sultone, to promote the stability of the catalyst and the good distribution of metal particles. Physicochemical characterizations revealed that the abundant synthesized metallic particles (mainly copper(I) oxide (Cu2O) although metallic copper particles were also present)) were of nanometric sizes. The catalyst was successfully applied for the catalytic reduction of three nitroaromatic compounds (4-nitrphenol, 4-chloronitroaniline, and 4-nitrocatechol). The variation of some experimental parameters was performed and marked effects on reaction rates were observed (increase with the catalyst concentration and decrease with the concentration of nitroaromatic compounds). An attempt to elucidate the mechanism of the catalytic reaction revealed that the adsorption of dihydrogen on the metal particles controlled the reaction rate while the adsorption of the nitroaromatic compounds controlled the induction time preceding the reduction reaction.

Diastereoselective cyclopropanation of α,β-unsaturated carbonyl compounds with vinyl sulfoxonium ylides.

Herein, we report a three-component stereoselective cyclopropanation of vinyl sulfoxonium ylides with indane 1,3-dione and aldehydes under mild reaction conditions. In contrast to previous reports, the present work shows that electrophilic addition selectively takes place at the α-position of the vinyl sulfoxonium ylide. The interesting feature of this approach is that the multicomponent reaction selectively proceeds because of the difference in nucleophilic reactivity of vinyl sulfoxonium ylides and indane 1,3-dione with electrophilic partners, such as aldehydes and in situ generated arylidenes. Additionally, density functional theory (DFT) studies were conducted to investigate the difference in the reactivity of these reactants, as well as to unveil the mechanism of this three-component reaction. Furthermore, non-covalent interactions of selectivity-determining transition states explain the origin of the diastereoselectivity of cyclopropanation.

A High-Performance Mn/TiO2 Catalyst with a High Solid Content for Selective Catalytic Reduction of NO at Low-Temperatures

Mn/TiO2 catalysts with varying solid contents were innovatively prepared by the sol–gel method and were used for selective catalytic reduction of NO at low temperatures using NH3 (NH3-SCR) as the reducing agent. Surprisingly, it was found that as the solid content of the sol increased, the catalytic activity of the developed Mn/TiO2 catalyst gradually increased, showing excellent catalytic performance. Notably, the Mn/TiO2 (50%) catalyst demonstrates outstanding denitration performance, achieving a 96% NO conversion rate at 100 °C under a volume hourly space velocity (VHSV) of 24,000 h−1, while maintaining high N2 selectivity and stability. It was discovered that as the solid content increased, the catalyst’s specific surface area (SSA), surface Mn4+ concentration, chemisorbed oxygen, chemisorption of NH3, and catalytic reducibility all improved, thereby enhancing the catalytic efficiency of NH3-SCR in degrading NO. Moreover, NH3 at the Lewis acidic sites and NH4+ at the Bronsted acidic sites of the catalyst were capable of reacting with NO. Conversely, NO and NO2 adsorbed on the catalyst, along with bidentate and monodentate nitrates, were unable to react with NH3 at low temperatures. Consequently, the developed catalyst’s low-temperature catalytic reaction mechanism aligns with the E-R mechanism.

Study on the Compressive Strength and Reaction Mechanism of Alkali-Activated Geopolymer Materials Using Coal Gangue and Ground Granulated Blast Furnace Slag

By reutilizing industrial byproducts, inorganic cementitious alkali-activated materials (AAMs) contribute to reduced energy consumption and carbon dioxide (CO2) emissions. In this study, coal gangue (CG) blended with ground granulated blast furnace slag (GGBFS) was used to prepare AAMs. The research focused on analyzing the effects of the GGBFS content and alkali activator (i.e., Na2O mass ratio and alkali modulus [SiO2/Na2O]) on the mechanical properties and microstructures of the AAMs. Through a series of spectroscopic and microscopic tests, the results showed that the GGBFS content had a significant influence on AAM compressive strength and paste fluidity; the optimal replacement of CG by GGBFS was 40–50%, and the optimal Na2O mass ratio and alkali modulus were 7% and 1.3, respectively. AAMs with a 50% GGBFS content exhibited a compact microstructure with a 28 d compressive strength of 54.59 MPa. Increasing the Na2O mass ratio from 6% to 8% promoted the hardening process and facilitated the formation of AAM gels; however, a 9% Na2O mass ratio inhibited the condensation of SiO4 and AlO4 ions, which decreased the compressive strength. Increasing the alkali modulus facilitated geopolymerization, which increased the compressive strength. Microscopic analysis showed that pore size and volume increased due to lower Na2O concentrations or alkali modulus. The results provide an experimental and theoretical basis for the large-scale utilization of AAMs in construction.

Enhanced Adsorption of Gaseous Naphthalene by Activated Carbon Fibers at Elevated Temperatures

This study utilized activated carbon fibers (ACFs) as adsorbents to investigate the removal efficiency of naphthalene and toluene at elevated temperatures and their competitive adsorption behavior. Three types of ACFs, inlet concentrations of naphthalene (343, 457, and 572 mg·Nm−3), and toluene (2055, 2877, and 4110 mg·Nm−3) were investigated to determine the adsorption capacities of naphthalene and toluene. To study the reaction mechanisms of naphthalene and toluene on the ACFs, the BET, SEM, FTIR, and TGA methods were used to examine the physical and chemical characteristics of ACFs. Results showed ACF-A’s superior adsorption capacity for naphthalene that was attributed to its mesoporous structure and hydrophobicity. Adsorption equilibrium studies indicated multilayer adsorption behavior. Competitive adsorption experiments demonstrated the displacement of toluene by naphthalene on ACF-A, highlighting its higher selectivity for naphthalene. Functional group analysis revealed changes in ACF surfaces after naphthalene adsorption, suggesting π-π dispersion and electron donor–acceptor interactions. Overall, this study underscores the importance of pore structure and surface properties in designing ACFs for the efficient adsorption of high-boiling-point organic pollutants.

Catalytic Deoxygenative Transformation of Ketoacids/Esters for the Synthesis of Coumarin, Benzofuranone, and Dihydrobenzo[b]oxepin‐2(3H)‐one Derivatives.

We disclose herein a triflic acid and silane‐promoted reductive deoxygenative transformation of ketoacid/esters for the divergent synthesis of different‐sized lactones, which hold substantial significance in pharmaceutical and natural product chemistry. Owing to the simple reaction conditions and setup, this protocol features broad substrate generality, scalability, and good functional group tolerance, including late‐stage functionalization of pharmaceutical compounds and natural products. The control experiments and detailed NMR study provide insight into the reaction mechanism.

Weak magnetic effect and free radical reaction mechanism on the dissolution of lightweight magnesia in CaO–Al2O3–SiO2 melts

Lightweight magnesia-based refractories play a crucial role in achieving energy savings and carbon reduction in steelmaking furnaces. The primary requirement is to make lightweight magnesia refractories with high corrosion resistance. The introduction of a weak static magnetic field is also a promising way to improve the slag resistance of lightweight refractories in addition to optimizing the composition and structure of the refractories. In this paper, the dissolution behavior of the lightweight magnesia in CaO–Al2O3–SiO2 molten slags at and above 1600 °C under weak static magnetic field is presented. The influence of the weak static magnetic field on the dissolution rate was analyzed, the behavior from the perspective of free radical and kinetics was discussed, and the influence of different calcia–silica weight ratios (C/S) on slag, magnetic flux density and the reaction mechanism are revealed. The results show that the dissolution rate of the lightweight magnesia in the molten slag presents a significantly weak magnetic effect, with a reaction inhibition interval of 2–4 mT in the range of 0–16 mT magnetic field intensity, and the key inhibition threshold surpasses that of alumina. The mechanism of the free radical formation and reaction during magnesia dissolution in high-temperature slag is explained and illustrated. The relationship between the magnetic flux density, superoxide radical content, and dissolution rate is presented, providing theoretical guidance for developing magnetic combined magnesia refractories.

Thermally stable high-loading single Cu sites on ZSM-5 for selective catalytic oxidation of NH3

Rigorous comparisons between single site- and nanoparticle (NP)-dispersed catalysts featuring the same composition, in terms of activity, selectivity, and reaction mechanism, are limited. This limitation is partly due to the tendency of single metal atoms to sinter into aggregated NPs at high loadings and elevated temperatures, driven by a decrease in metal surface free energy. Here, we have developed a unique two-step method for the synthesis of single Cu sites on ZSM-5 (termed CuS/ZSM-5) with high thermal stability. The atomic-level dispersion of single Cu sites was confirmed through scanning transmission electron microscopy, X-ray absorption fine structure (XAFS), and electron paramagnetic resonance spectroscopy. The CuS/ZSM-5 catalyst was compared to a CuO NP-based catalyst (termed CuN/ZSM-5) in the oxidation of NH3 to N2, with the former exhibiting superior activity and selectivity. Furthermore, operando XAFS and diffuse reflectance infrared Fourier transform spectroscopy studies were conducted to simultaneously assess the fate of the Cu and the surface adsorbates, providing a comprehensive understanding of the mechanism of the two catalysts. The study shows that the facile redox behavior exhibited by single Cu sites correlates with the enhanced activity observed for the CuS/ZSM-5 catalyst.

A Room-Temperature All-Solid-State Na-Ag Battery with a Long Cycle Life and Low Overpotential.

Aqueous Zn-Ag batteries have been developed and commercialized for nearly a century, offering stable discharge and high specific energies. Sodium, with its lower redox potential, smaller charge-to-mass ratio, and abundant resources, presents a promising alternative to zinc. In this study, we successfully developed an all-solid-state Na-Ag battery system. This battery demonstrates stable discharge and charge voltages, low overpotential (0.27 V), high energy efficiency (>91%), and long cycle life under moderate humidity at room temperature. The reaction mechanism was elucidated through combined analyses using differential electrochemical mass spectrometry (DEMS), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Our findings indicate that metallic Ag in the cathode materials acts as an effective catalyst for the oxygen reduction reaction during the initial discharge process, forming NaOH as the discharge product. Ag is then oxidized during the charging process and recovered during discharge, serving as an active reactant in the Na-Ag battery. This work demonstrates superior performance of all-solid-state Na-Ag battery over aqueous Zn-Ag battery. Na-Ag battery may be of interest in applications with stringent requirements on stable discharge voltage and high specific energy.

Hydrogenation of hexene catalyzed by a ruthenium (II) complex with N‐heterocyclic carbene ligands

AbstractIn this study, we investigated the mechanism of the inactivated hexene hydrogenation reaction catalyzed by a ruthenium (II) complex containing “N‐heterocyclic carbene” (NHC) ligands, specifically SIMes and CBA, using DFT calculations. Our focus was on RuH(OSO2CF3)(CO)(SIMes)(CBA), which exhibits excellent catalytic behavior. We tested the B3LYP‐D3, cam‐B3LYP, and TPSSh functionals. The hydrogenation reaction is initiated by the release of SIMes rather than CBA due to the lower associated dissociation energy. Our findings indicate a reaction mechanism consisting of two consecutive steps, each involving one hydrogen atom migration. The first step, considered as the kinetically limiting transition state, exhibits a Gibbs free activation barrier of 12.9 kcal mol−1. This step involves two asynchronous processes. The first one describes the migration of the ruthenium hydride to the internal carbon of the olefine function, transitioning from π to σ coordination mode, which promotes the formation of a bond between ruthenium and the terminal olefinic carbon. The second process involves the oxidation of ruthenium from Ru(II) to Ru(IV). This oxidation is crucial as it enables the decomposition of the H2 molecule into two hydrogen atoms bonded to the ruthenium atom. The geometrical structures of the Hidden Reaction Intermediate Ru(II) complex and the quasi‐transition state of the second process have been determined by means of the RIRC technique. The second step entails the migration of one of the newly formed hydrides of the Ru(IV) complex to the terminal olefinic carbon, resulting in the release of hexane with a weak activation Gibbs free energy of .8 kcal mol−1. Lastly, we explored the use of dichloromethane as a solvent, considering the PCM model. The presence of the solvent significantly decreases the energy dissociation of SIMes from 17.9 to 9.0 kcal mol−1, providing notable benefits.

Efficient preparation of cellulose nanocrystals and regulation of cholesteric liquid crystals for advanced anti‐counterfeiting

AbstractCellulose nanocrystals (CNCs) can self‐assemble to form cholesteric liquid crystal, which make it one of the most promising optical materials at present. CNCs can be produced by sulfuric acid hydrolysis. It is found that hydrolysis conditions influence the existing form of reaction components and their reaction activities, which leads to different reaction routes and mechanisms under varied reaction conditions, with CNCs of varied quality produced. High‐quality CNC with more uniform particle size could be prepared at a critical acid concentration of 64 wt%, which was used to study the formation process of CNC liquid crystal and the structure regulation of cholesteric liquid crystal. By adjusting the drying temperature and adding a small molecule of water‐soluble chitosan (WSC) can well regulate cholesteric liquid crystal and change the pitch of a film, and the reflection wavelength can be redshifted, thus enriching texture patterns and creating distinctive color. Suitable addition of WSC can enhance the multi‐domain effect during liquid crystal formation process and finally creates more colorful film with fine texture. The rich and tunable liquid crystal characteristics endowed by WSC addition is irreplicable and artistic, which helps to realize the great potential application of the composite film in advanced anti‐counterfeiting.

Cascade Oxypalladation/1,3-Palladium Shift to Access Cyclopentene-Fused Isocoumarins.

Fused isocoumarins are frequently found in several natural products and pharmaceuticals. Herein, a cascade annulation of 2-alkynylbenzoate-tethered cyclic 1,3-diones via sequential trans-oxypalladation, carbonyl insertion, 1,3-Pd shift, and β-hydride elimination is reported. This method provides efficient access to highly diastereoselective tetracyclic cyclopentene-fused isocoumarins containing two contiguous quaternary stereocenters. A plausible reaction mechanism is proposed on the basis of mechanistic studies, including deuterium labeling experiments. Studies toward enantioselective synthesis using a chiral Bpy ligand gave encouraging initial results.