Organic luminescent radicals have attracted considerable research interest owing to their unique doublet-state emission characteristics and the potential for achieving high exciton utilization efficiencies. In these systems, the two lowest-energy excitation pathways typically involve α-type [singly occupied molecular orbital (SOMOα) to lowest unoccupied molecular orbital (LUMOα)] and β-type [highest occupied molecular orbital (HOMOβ) to singly unoccupied molecular orbital (SOMOβ)] transitions. Elucidating the fundamental differences between these two transition types is crucial to assess how a pathway switch impacts luminescence efficiency. In this work, we employed density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, combined with the thermal vibration correlation function (TVCF) method, to systematically investigate α-type transitions in a series of reported acceptor-controlled bis(2,4,6-trichlorophenyl)methyl (BTM) radicals containing carbazolyl (Cz) or N-pyrido[3,4-b]indolyl (PyID) units (2CNPh/NO2Ph/2NO2Ph-Cz/PyID-BTM). Furthermore, we extended this strategy to COCF3Ph-substituted derivatives (COCF3Ph/2COCF3Ph-Cz/PyID-BTM) and introduced triphenylamine (TPA) donor groups to recover β-type transitions, thereby enabling a direct comparison between transition pathway selection and luminescence efficiency for a total of 16 systems. Results indicate that strong acceptor substitution significantly lowers the LUMOα energy level and reduces the gap between LUMOα and SOMOα, facilitating α-type excitation from the ground doublet state (D0) to the first excited doublet state (D1). Although this β → α switching enhances the radiative decay rate, the resulting α-type systems still exhibit relatively large non-radiative decay rates (knr ∼ 109 s−1), indicating that transition-type switching alone is insufficient to ensure high luminescence efficiency. In contrast, TPA-substituted derivatives retain β-type transitions while further suppressing knr to the order of 108 s−1 and increasing kr. These improvements lead to estimated photoluminescence quantum yields of 7.1% (TPA-PyID-BTM), 10.5% (TPA-Cz-BTM), 16.2% (2TPA-PyID-BTM), and 17.2% (2TPA-Cz-BTM), compared with 0.024% (Cz-BTM) and 0.15% (PyID-BTM) for the parent systems. These results show that luminescence efficiency is governed not simply by transition type, but more critically by substituent-driven excited-state electron redistribution and modulation of vibronic coupling. Our study elucidates how transition type and non-radiative decay jointly govern luminescence efficiency in radical systems, providing theoretical guidance for the molecular design and performance optimization of organic radicals.

Organic room temperature phosphorescent (RTP) materials have attracted considerable interest owing to their unique luminescence properties and broad application potential. Among various design strategies, such as host-guest doping, crystallization, and heavy-atom incorporation, substituent engineering has emerged as a particularly efficient approach for tuning RTP performance. Herein, we systematically investigate the origin of the enhanced phosphorescence in 9-TI (4-[1-Naphthyl]-N,N-diphenylaniline) relative to its analogue 8-TI (4[Isoquinolin-8-yl]-N,N-diphenylaniline) through the introduction of a planarizing substituent. Our multiscale analysis integrates molecular geometry, electronic structure, excited state dynamics, and electron vibrational coupling. Detailedly, their luminescence properties are studied by first-principles calculations, the molecular stacking configurations and photophysical properties are simulated by density functional theory (DFT) and timedependent density functional theory (TD-DFT) methods with the quantum mechanics and molecular mechanics (QM/MM) model. Structurally, 9-TI exhibits improved substituent and partial molecular planarity, which promotes It-conjugation and restricts non-radiative decay caused by molecular vibrations. Its crystal environment is characterized by a larger free volume and predominance of weak H-H interactions, collectively mitigating aggregation-caused quenching. Electronically, the near absence of n-orbital character in the molecular orbitals of 9-TI, together with enhanced It-It* delocalization and orbital localization, facilitates efficient spin-orbit coupling (SOC). Additionally, 9-TI possesses a larger singlet triplet energy gap (Delta EST = 1.55 eV), which suppresses reverse intersystem crossing (kRISC = 1.31 & times; 10-3 s- 1). In the kinetic competition between radiative (kr) and nonradiative (knr) decay, 9-TI exhibits effective suppression of knr (2.71 & times; 103 s-1), favoring phosphorescence emission. This is further corroborated by its lower Huang-Rhys factor and reduced reorganization energy, indicating diminished electron vibrational coupling and associated non-radiative losses. Furthermore, our designed 9-TI compound is demonstrated to be a more efficient RTP molecule with a longer exciton lifetime (1600 mu s) compared to that of 8-TI (18 mu s). In summary, the superior RTP performance of 9-TI arises from a synergistic optimization across molecular geometry, electronic orbital characteristics, excited state dynamics, and vibrational activity. Our work provides a theoretical foundation for the rational design of high-performance pure organic RTP materials through targeted substituent modification.

ABSTRACT The depressing of atmospheric CO 2 concentration necessitates sustainable chemical conversion strategies by direct hydrogenation to light alkanes (C 2 0 ‐C 4 0 ) over oxide/zeolite (OXZEO) bifunctional catalyst. Prior studies demonstrated that SSZ‐13 aluminosilicate with strong acidity as zeolite component promotes hydrogen transfer to yield alkanes but also accelerates coking/deactivation, while SAPO‐34 silicoaluminophosphate with moderate acidity greatly improves the catalytic stability but yields insufficient alkane selectivity. Herein, we designed a new OXZEO bifunctional catalytic system based on trace Platinum species (0.11 wt.%) confined within SAPO‐34 coupling with ZnZrO x solid solution (ZnZrO x /Pt@SAPO‐34), achieving a high CO 2 conversion (46.1%) with C 2 0 ‐C 4 0 selectivity (94.1%), and giving a superior stable lifetime over 200 h. The excellent catalytic performance is attributed to the confined hydrogen spillover mechanism over Pt species in SAPO‐34 that suppresses carbon deposition and enables efficient H 2 dissociation and spillover to significantly promote light olefin hydrogenation to corresponding alkanes.

Hydrostatic pressure provides a powerful external stimulus to modulate the excited-state properties of organic room-temperature phosphorescent (RTP) materials, yet the microscopic origin of pressure-induced spectral evolution remains insufficiently understood. Herein, we present a comprehensive theoretical investigation into the origin of blue-shifted RTP emission in IH-MPT under hydrostatic pressure. The calculations reveal that increasing pressure induces a pronounced blue shift in the phosphorescence spectrum, which originates from a continuous upward shift of the lowest triplet excited state (T1) energy level rather than aggregation or excimer effects. Structural analyses show that pressure progressively enhances molecular rigidity through packing densification and intramolecular planarization, effectively suppressing excited-state geometric relaxation. Consistently, the excited-state wave function becomes increasingly localized, accompanied by reduced vibronic coupling, decreased Huang-Rhys factors, and lower reorganization energies. Dimer calculations and Hirshfeld surface analyses further confirm that intermolecular electronic coupling is negligible and that the emission modulation is dominated by intrinsic monomer behavior reinforced by pressure-enhanced intermolecular constraints. Notably, an optimal pressure of approximately 16 GPa is identified, at which IH-MPT exhibits the bluest emission and simultaneously maximizes intersystem crossing and radiative decay rates. This optimal behavior arises from a synergistic balance between molecular rigidification and favorable energetic matching in the excited-state relaxation process, whereas excessive compression disrupts this balance and reduces emission efficiency. These results elucidate the mechanistic origin of pressure-regulated RTP emission and provide valuable insights into the rational control of phosphorescence through external pressure.

The rational design of stimuli-responsive organic room-temperature phosphorescence (RTP) materials is often hindered by an incomplete understanding of the intricate interplay between molecular structure, crystal packing, and excited-state dynamics, particularly in polymorphic systems. Clarifying how subtle structural variations govern photophysical properties is crucial for advancing tunable luminescent materials. Herein, we systematically investigate the dual-emission mechanism and pressure-responsive behavior of a polymorphic RTP material, BrTA-F, in its two crystalline phases (Cry-A and Cry-B), using density functional theory (DFT) and time-dependent density functional theory (TDDFT) combined with quantum mechanics and molecular mechanics methods (QM/MM) and thermal vibration correlation function (TVCF) methods. The results reveal that the distinct spatial distribution of fluorine (F) atoms modulates intermolecular interactions and molecular planarity, leading to different hydrogen bond strengths and excited-state characteristics between the two polymorphs. The dual-RTP emission in Cry-B is attributed to competitive radiative decay from the monomeric first (T1) and second (T2) triplet excited state, which is facilitated by enhanced spin orbit coupling (SOC) resulting from variations in n-π*/ππ* transition proportions. Furthermore, Cry-A demonstrates high sensitivity to hydrostatic pressure, which tunes the emission wavelength and decay rates by compressing the lattice and altering intermolecular force balances. This work provides fundamental insights into the structure-property relationships in polymorphic RTP systems and offers guidance for designing stimuli-responsive luminescent materials.

Organic room-temperature phosphorescence (RTP) emitters with long lifetimes, high exciton utilizations, and tunable emission properties show promising applications in organic light-emitting diodes (OLEDs) and biomedical fields. Their excited-state properties are highly related to single molecular structure, aggregation morphology, and external stimulus (such as hydrostatic pressure effect). To gain a deeper understanding and effectively regulate the key factors of luminescent efficiency and lifetime for RTP emitters, we employ the thermal vibration correlation function (TVCF) theory coupled with quantum mechanics/molecular mechanics (QM/MM) calculations to investigate the photophysical properties of three reported RTP crystals (Bp-OEt, Xan-OEt, and Xan-OMe) with elastic/plastic deformation. By analyzing the geometric structures and stacking modes of these crystals, we observe that the geometric structure variations influence the electronic structures, subsequently modifying the transition properties and the energy consumption processes. Specifically, the presence of strong pi-pi interactions and hydrogen bonds in the Xan-OEt crystal inhibits a nonradiative decay process, thereby realizing long-lived emission. Additionally, the hybridized local and charge-transfer (HLCT) excited-state feature with the largest charge transfer excitation contributions (57.74%) for Xan-OEt stabilizes the triplet excitons and facilitates the radiative decay process, ultimately achieving high efficiency and long lifetime emissions. Furthermore, by applying high hydrostatic pressure for the Bp-OEt crystal, the RTP emission efficiencies and lifetimes are enhanced and blue-shifted. All of these results demonstrate the crucial role of molecular structure and stacking modes as well as the hydrostatic pressure effect in regulating RTP properties. Thus, our findings reveal the structure-packing-property relationship and highlight the control of molecular packing and the related tunable approaches, which could provide prospective strategies for constructing stimuli-responsive RTP emitters in practical applications.

Nonmonotonic pressure-dependent luminescent efficiency is commonly observed in inorganic systems. In contrast, organic room-temperature phosphorescence (RTP) materials exhibiting monotonic efficiency enhancement remain scarce, with the underlying mechanisms being poorly understood. Herein, we present a comprehensive theoretical investigation of pressure-induced RTP dynamics in organic crystals, which not only advances the fundamental understanding of excited-state processes but also paves the way for high-precision pressure-sensing applications. We systematically elucidate the intricate relationship among hydrostatic pressure, molecular packing, and photophysical properties by combining thermal vibration correlation function (TVCF) theory with quantum mechanics/molecular mechanics (QM/MM) simulations. In PFP-F crystalline aggregates, pressure-induced densification results in a slight blue shift accompanied by monotonic enhancements in the RTP efficiency and lifetime. These phenomena are attributed to accelerated radiative decay rates (kr) due to the pressure-enhanced spin-orbit coupling (SOC) effect, suppressed nonradiative transitions through closer π-π stacking, restricted geometric changes, and reduced root-mean-square displacement (RMSD) values. The pressure-tunable π-stacking geometry in PFP-F crystals enables precise control over SOC constants and energy levels, facilitating monotonic efficiency optimization. Furthermore, strengthened intermolecular interactions under compression provide efficient channels for the excited-state energy consumption process, significantly minimizing the nonradiative decay rate. These findings offer profound mechanistic insights into pressure-induced RTP properties and establish design principles for developing piezochromic luminescent materials with tailored optoelectronic properties.

Organic room-temperature phosphorescence (RTP) materials hold promising applications in the field of display technologies and information encryption. Achieving efficient RTP emission relies on precisely regulating excited-state properties and luminescence pathways. In this study, three experimentally reported donor-acceptor molecules are selected, and the effects of oxidation on their photophysical properties are systematically investigated by first-principles calculations. The results show that oxidation of the donor units effectively modulates intramolecular charge transfer characteristics and the excited state energy levels, thereby influencing the reverse intersystem crossing (RISC) and exciton transfer processes, related thermally activated delayed fluorescence (TADF) and RTP emission mechanisms are revealed. Among the studied molecules, the fully oxidized molecule DOPTZ-CO exhibits the most favorable RTP performance. Using DOPTZ as the oxidized donor, three molecules featuring pronounced n-π* transition characteristics are further designed, and a novel strategy is proposed to regulate emission pathways by incorporating non-bonding (n) orbitals. The introduction of n-π* transition is found to play a dual role: it enhances spin-orbit coupling (SOC) effect, facilitating radiative T1-S0 transitions and it also increases the S1-T1 energy gap (ΔEST), thereby suppressing RISC process and favoring RTP-dominated emission. Thus, molecules with moderate ΔEST values (approximately 0.4 eV) and strong n-π* character demonstrate efficient and controllable RTP behavior. Overall, this study underscores the critical role of excited-state modulation and orbital engineering in tuning emission pathways and provides a theoretical foundation for the rational design of high-performance organic RTP materials.

Stimulus-responsive organic room temperature phosphorescence (RTP) materials are a class of materials that show emission property changes when subjected to diverse environmental stimuli. The change of molecular stacking modes and intermolecular interactions can result in mechanical stimulus-induced emission switching behaviour. The underlying mechanism of mechanoresponsive luminescent material is still unclear. Herein, based on density functional theory and time-dependent density functional theory calculations, the photophysical properties with response to hydrostatic pressure of RTP molecules in crystal are theoretically studied. Excited state dynamic processes are investigated by using quantum mechanics and molecular mechanics method coupled with thermal vibration correlation function method. Results show that the increase of pressure can blue-shift the RTP emissions which is mainly caused by the change of molecular conformation and the increase of bending vibration frequency. Under 2 Gpa, large spin-orbit coupling effect is determined, remarkable radiative and non-radiative decay processes are achieved. At 0.6 Gpa, a small non-radiative decay rate from T-1 to S-0 is obtained, high efficiency and long lifetime (more than 10 times the other pressures) are realised. Through further analysing the staking modes, reorganisation energies and SOC constants, relationships between molecular structures and RTP properties are determined, hydrostatic pressure responsive mechanism is revealed. [GRAPHICS]

The nucleophilic activation of ketones containing a tethered hydroxyl group by borinic acid, through the formation of an unprecedented tetracoordinated boron enolate complex, is presented. The in situ-generated boron enolates are captured by electrophilic isatin imines, which are activated by chiral copper-based catalysts. This reaction accommodates a wide range of substrates, producing a series of 3-substituted 3-amino-2-oxindoles with a C3-tetrasubstituted stereogenic center, all in excellent yields and enantioselectivities. The method's utility is further demonstrated by a gram-scale reaction and subsequent elaboration of the Mannich adducts.

Stimulus-responsive organic room temperature phosphorescence (RTP) materials exhibit variations in their luminescent characteristics (lifetime and efficiency) upon exposure to external stimuli, including force, heat, light and acid-base conditions, the development of stimulus-responsive RTP molecules becomes imperative. However, the inner responsive mechanism is unclear, theoretical investigations to reveal the relationship among hydrostatic pressures, molecular structures and photophysical properties are highly desired. Herein, taking the Se-containing RTP molecule (SeAN) as a model, based on the dispersion corrected density functional theory (DFT-D), the combined quantum mechanics and molecular dynamics (QM/MM) method and thermal vibration correlation function (TVCF) theory, the influences of hydrostatic pressure on molecular structures, transition properties as well as lifetimes and efficiencies of RTP molecule are theoretically studied. Results show that extended lifetime and enhanced efficiency are observed at 2 Gpa compared with molecule at normal pressure, and this is related with the small reorganization energy and large oscillator strength. Moreover, due to the small energy gap (0.34 eV) and remarkable spin-orbit coupling (SOC) constant (8.56 cm-1) between first singlet excited state and triplet state, fast intersystem crossing (ISC) process is determined for molecule at 6 Gpa. Furthermore, the intermolecular interactions are visualized using independent gradient model based on Hirshfeld partition (IGMH) and the changes of molecular packing modes, SOC values, lifetimes and efficiencies with pressures are detected. These results reveal the relationship between molecular structures and RTP properties. Our work provides theoretical insights into the hydrostatic pressure response mechanism and could promote the development new efficient stimulus-responsive molecules.

Since room temperature phosphorescence (RTP) molecules typically exhibit small spin-orbit coupling (SOC) effect and a rapid non-radiative decay process, achieving efficient RTP emission is challenging. Therefore, it is imperative to enhance the SOC constant to facilitate efficient RTP and related structure-property relationship needs to be clarified. Herein, based on first-principle calculations, this paper elucidates the impact of molecular folding structure on SOC and RTP efficiency, excited state properties and exciton conversion processes are detailed studied. Results indicate that both the heavy atom effect and folding degree affect the SOC constants and the latter factor plays a dominate role than the former for studied systems. In addition, the intermolecular interactions can inhibit the geometric changes, decrease the reorganisation energies and increase transition dipole moment, thus the radiative decay rates are increased and non-radiative decay rates are decreased, efficient RTP emissions are realised for TA and PX molecules, no emission feature is determined for DX, previous experimental measurements are reasonably illustrated. These findings reveal the inner relationship among molecular folding structure, environmental effects and RTP performance. This study offers a theoretical perspective for elucidating the mechanism underlying fold-induced RTP enhancement, which provides an innovative molecular design strategy for developing efficient RTP emitters.

Development of sustainable synthetic methods for the hydrosilylation of alkenes, catalyzed by 3d transition metals, offers a promising alternative to traditional noble metal catalysts. This study presents a computational mechanistic investigation into the hydrosilylation of alkenes, focusing on the role of ligands and metal centers in modulating the reaction's mechanism and regioselectivity. The ligand's electronic and steric properties were found to modulate the regioselectivity for cobalt catalysts, with phosphine ligand (xantphos) promoting higher linear selectivity compared to nitrogen-based ligand (mesPDI). The energy decomposition analysis reveals that the xantphos ligand favors linear products due to stronger electrostatic and orbital interactions despite increased steric repulsion. The metal center also plays a crucial role, with cobalt catalysts favoring the modified Chalk-Harrod mechanism for branched product formation in the presence of PNN ligand (iPrPCNNMe), due to lower activation barriers in alkene insertion. Beneficial electrostatic and orbital interactions predominate, rendering the alkene insertion transition state for cobalt more favorable compared to that for iron. This work provides a comprehensive understanding of how ligand and metal center effects can be harnessed to control regioselectivity in hydrosilylation reactions.

Red and deep red (DR) organic light-emitting diodes (OLEDs) have garnered increasing attention due to their widespread applications in display technology and lighting devices. However, most red OLEDs exhibit low luminescence efficiency, severely limiting their practical applications. To address this challenge, we theoretically design four novel TADF molecules with red and DR luminescence using intramolecular locking strategies building upon the experimental findings of DCN-DLB and DCN-DSP, and their crystal structures are predicted with the lower energy and higher packing density. The photophysical properties and luminescence mechanism of six molecules in toluene and crystal are clarified using the first principles calculation and thermal vibration correlation function (TVCF) method. The proposed design strategy is anticipated to offer several advantages: enhanced electron-donating capabilities, more rigid structures, longer emission wavelengths and higher luminescence efficiency. Specifically, we introduce oxygen atoms and nitrogen atoms as intramolecular locks, and the newly developed DCN-DBF and DCN-PHC have redshifted emission, narrow singlet-triplet energy gap (ΔEST), fast reverse intersystem crossing rate and enhanced photoluminescence quantum yield (PLQY). Notably, DCN-DBF achieves both long wavelength emission and high efficiency, with emission peaks at 598 nm and 587 nm corresponding to PLQY of 52.13 % and 43.42 % in toluene and crystal, respectively. Our work not only elucidates the relationship between molecular structures and photophysical properties, but also proposes feasible intramolecular locking design strategies and four promising red and DR TADF molecules, which could provide a valuable reference for the design of more efficient red and DR TADF emitters.

BACKGROUNDThe ester-synthesis enzymes influenced by environmental factors during Daqu-making process largely determine the flavor of Chinese liquor, but the main ester-synthesis enzyme and its key influencer remain unclear. Here, the volatile ester profiles over the whole Daqu-making process, under different treatments, for at least 90 days, were carefully analyzed, and the potential ester-synthesis enzymes, as well as their dependently environmental factors, were explored. RESULTSIn the detected 46 volatile esters, only the short-chain (C4-C8) and medium-chain (C9-C13) ester content obviously changed, as the primary contributor discriminating different samples. Their trends were both consistent with that of the alcohols and the primary metabolism, which included alcohol acyltransferases (AATs) reaction with alcohols and acyl-CoAs as the substrates. Among the potential ester-synthesis enzymes, the typical AAT activity also exhibited the highest correlation with the short- and medium-chain esters (r > 0.78, P < 0.05). The Mantel test between environmental factors and ester production showed that temperature of Daqu was directly correlated with the short-chain esters (r = 0.58, P < 0.01) and AAT activity (r = 0.56, P < 0.01). Further, the short- and medium-chain ester content in Daqu under the treatment nearer to the reported optimal temperature of 40-50 degrees C of AATs reaction was overall higher than that of the other treatment Daqu. CONCLUSIONThis study revealed that the temperature-dependent AATs reaction was the main enzymatic method producing the short- and medium-chain esters over the whole Daqu-making process. The results could contribute to the flavor improvement of Baijiu. (c) 2022 Society of Chemical Industry.

Purely organic room temperature phosphorescence (RTP) materials have garnered extensive attentions in anti-counterfeiting and encryption, information display, biological imaging and organic light emitting diodes (OLEDs) due to the features of long lifetimes, low toxicity and good biocompatibility. Nevertheless, both the species and amounts of the efficient RTP molecules are far from meeting the requirements for practical applications, and the quantitative relationship between molecular structures and optoelectronic properties needs full elucidated. Herein, the photophysical properties and properties of three isomers (o-BA, m-BA and p-BA) are explored based on the first-principles calculations coupled with thermal vibration correlation function (TVCF) method and kinetic Monte Carlo simulations. The substituent effects on the molecular structures, intermolecular interactions, transition properties, Huang-Rhys factors and reorganization energies, excited state dynamics as well as transfer integrals and charge carrier mobilities are investigated in detail to clarify the structure-property relationships. Results show that o-BA achieves fast radiative rate on account of impressive transition dipole moment and oscillator strength, but equally large non-radiative decay rate leads to low RTP efficiency. Promisingly, the highest holes mobility is determined for o-BA due to the largest transfer integrals of holes originating from the strong intermolecular interactions. In addition, compared with o-BA and p-BA, m-BA could achieve fast intersystem crossing (ISC) rate with large spin orbit coupling constant and low non-radiative decay rate with small geometric structure changes. Relatively balanced holes and electrons mobilities of m-BA have been demonstrated, which contributes to the recombination of excitons and the improvement of luminescence efficiency. For p-BA, the strong intermolecular hydrogen bonding restricts the free rotation of single bonds and promotes the molecular coplanarity, which contributes to efficient emission. Furthermore, the charge mobility is calculated and the temperature dependence is investigated, the hopping mechanisms for studied isomers are illustrated. This work reveals the relationship among molecular structures, crystal packing modes, photophysical properties and charge transport properties of isomers, and provides an insight for molecular design and property prediction.

A diastereodivergent asymmetric desymmetrization of azetidinium salts with benzothiazoleamides as carbon nucleophiles through a chiral N,N'-dioxide/Mg(II) complex-promoted ring-opening reaction is realized by tuning ligands. Both syn- and anti-chiral δ-amino acid derivatives bearing benzothiazole structure were obtained in moderate to good yields and dr and ee values. DFT calculations indicated that the diastereodivergency stems from the different size of the chiral pocket formed by variable substructures of the ligands, leading to the opposite attack direction of the nucleophiles.

Asymmetric synthesis of enantioenriched azo compounds bearing tetrasubstituted stereocenter was achieved through chiral N,N′-dioxide/metal Lewis acid promoted interrupted Japp-Klingemann reaction of aryldiazonium tetrafluoroborate salts with nucleophiles under mild conditions. This protocol features wide substrate scope and good functional group compatibility. Azaarene-containing chiral azo compounds were stable enough in Japp-Klingemann reaction condition. The key to success of the reaction was the employment of metal salt/N,N′-dioxide ligand and the dual-task roles of the base. Moreover, the X-ray crystal structure of Ni(II)/N,N′-dioxide/substrate complex confirmed that the substrate was activated by bidentate coordination, which shed light on the origin of chiral control of the reaction.

A novel and convenient palladium-catalyzed cascade 5-exo-trig radical cyclization/aromatic C-H alkylation with unactivated alkyl iodides has been described. This strategy provides an efficient access to a variety of 3a-methyl-1,2,3,3a,4,8b-hexahydroindeno[1,2-b]pyrrole derivatives, which facilitate access to a series of medically important heterocyclic bioactive molecules. This protocol involves mild catalytic reaction conditions and shows high functional group tolerance with high stereoselectivity. Mechanistic investigations reveal that an alkyl radical pathway is involved in this reaction.

An efficient asymmetric acyl-Mannich reaction of isoquinolines with α-(diazomethyl)phosphonate and diazoacetate has been developed using chiral spiro phosphoric acids as catalysts. This reaction allowed the construction of a series of chiral 1,2-dihydroisoquinolines bearing a tertiary stereocenter at the C1 position with up to 98% yield and 99% ee.