Bond Cleavage Process Research Articles

Photoinduced Radical Approach for Desulfurative Alkylation of Cysteine Derivatives to Make Unnatural Amino Acids.

Unnatural amino acids (UAAs) are highly valuable molecules in organic synthesis, pharmaceutical sciences, and material science. Herein, we present a photocatalytic radical approach for desulfurative alkylation of cysteine derivatives with arenethiol as the hydrogen atom transfer catalyst for making UAAs and peptides. The formate salt, acting as the hydrogen atom donor, in situ generates the highly reductive CO2 radical anion species, which is the key to unlocking the C-S bond cleavage process with a simple benzoyl protecting group. No photocatalyst is required for the radical initiation and propagation, which makes such a visible-light-induced process mild, efficient, and sustainable.

Nitrate Enhanced Sulfamethoxazole Degradation by 222 nm Far-UVC Irradiation: Role of Reactive Nitrogen Species.

The application of 222 nm far-UVC irradiation for degrading organic micropollutants in water shows promise. Nitrate (NO3-), found in nearly all water bodies, can significantly impact the performance of 222 nm far-UVC-driven systems. This work was the first to investigate the effect of NO3- on sulfamethoxazole (SMX) photodegradation at 222 nm, finding that NO3- significantly enhances SMX degradation in different dissociated forms. Besides the hydroxyl radical (•OH), reactive nitrogen species (RNS) also played important roles in SMX degradation. With increasing NO3- concentration, the RNS contribution to SMX degradation decreased from 25.7 to 8.6% at pH 3 but increased from 1.5 to 24.7% at pH 7, since the deprotonated SMX with electron-rich groups reacted more easily with RNS. The transformation mechanisms of SMX involving isomerization, bond cleavage, hydroxylation, nitrosation, and nitration processes were proposed. 15N isotope labeling experiments showed that the RNS-induced nitrated products even became the major products of SMX in the 222 nm far-UVC/NO3- system at pH 7 and exhibited a higher toxicity than SMX itself. Further research is necessary to avoid or eliminate these toxic byproducts. This study provides valuable insights for guiding the utilization of 222 nm far-UVC for treating antibiotics in NO3--containing water.

Intramolecular Carboamination of Aminodienes to N-Heterocycles via C-N Bond Activation.

The catalytic transformation of ubiquitous but inert C-N bonds is highly appealing in synthetic chemistry, but the efficient cleaving inert C-N bond and simultaneous incorporation of both the cleaved C-moiety and N-moiety into the desired products has been a long-standing formidable challenge so far. Here, we developed a radical-addition triggered cyclization and C-N bond cleavage process enabled by the unique I2 /Ni or benzyl halide/Ni-catalytic system, allowing the formal insertion of diene into the inert C-N bond. This reaction features high atom economy and enables an expedient annulative carboamination of aminodienes to diverse pyrrolidines, piperidines, and tetrahydroisoquinolines. Mechanistic studies have revealed that the reaction is initiated via the generation of a benzyl radical and the formation of quaternary ammonium salt is key for the C-N bond cleavage.

Intramolecular Carboamination of Aminodienes to N‐Heterocycles via C−N Bond Activation

AbstractThe catalytic transformation of ubiquitous but inert C−N bonds is highly appealing in synthetic chemistry, but the efficient cleaving inert C−N bond and simultaneous incorporation of both the cleaved C‐moiety and N‐moiety into the desired products has been a long‐standing formidable challenge so far. Here, we developed a radical‐addition triggered cyclization and C−N bond cleavage process enabled by the unique I2/Ni or benzyl halide/Ni‐catalytic system, allowing the formal insertion of diene into the inert C−N bond. This reaction features high atom economy and enables an expedient annulative carboamination of aminodienes to diverse pyrrolidines, piperidines, and tetrahydroisoquinolines. Mechanistic studies have revealed that the reaction is initiated via the generation of a benzyl radical and the formation of quaternary ammonium salt is key for the C−N bond cleavage.

DFT study on isothiourea-catalyzed C-C bond activation of cyclobutenone: the role of the catalyst and the origin of stereoselectivity.

The organocatalytic C-C bond activation strategy stands out as a new reaction mode for the release of ring strain and expands the scope of organocatalysts. Thus, disclosing the role of the organocatalyst in the C-C bond cleavage process would be of interest. Here, an isothiourea-catalyzed C-C bond activation/cycloaddition reaction of cyclobutenone is selected as a computational model to uncover the role of the catalyst. Based on the calculations, the electrocyclic cleavage of cyclobutenone is calculated to be energetically more favorable than the isothiourea-catalyzed C-C bond cleavage, which is different from the NHC-catalyzed C-C bond activation of cyclobutenone. The computational results show that the isothiourea promotes the reaction by increasing the nucleophilicity of vinyl ketene and thus lowers the energy barrier of the cycloaddition process. Moreover, NCI and AIM analyses are performed to disclose the origin of stereoselectivity.

Multielectron Bond Cleavage Processes Enabled by Redox-Responsive Phosphinimide Ligands.

The activation of small molecules via multielectron redox processes offers promise in mediating difficult transformations related to energy conversion processes. While molecular systems that engage in one- and two-electron redox processes are widespread, those that participate in the direct transfer of four or more electrons to small molecules are very rare. To that end, we report a mononuclear CrII complex competent for the 4-electron reduction of dioxygen (O2) and nitrosoarenes. These systems additionally engage in facile two-electron group transfer reactivity, including O atom excision and nitrene transfer. Structural, spectroscopic, and computational studies support bond activation processes that intimately occur at a mononuclear chromium(phosphinimide) center and highlight the unusual structural responsiveness of the phosphinimides in stabilizing a range of metal redox states.

Four - Electron Oxidative Addition of an N=N Double Bond at a Chromium Metallocyclopropene.

This report describes the synthesis of a pseudo-tetrahedral chromium alkyne complex supported by a bidentate phosphinimide ligand and its reactivity with azobenzene. Characterization of the former by structural and computational methods reveals an unprecedented extent of alkyne activation by a formal chromium(II) center, suggesting that this complex is best described as a chromium(IV)-metallocyclopropene. Exposure of this compound to an azobenzene derivative results in the formation of a chromium(VI) diimido complex, which constitutes a rare 4-electron oxidative addition of an N=N double bond. The isolation of a chromium(IV)-hydrazido intermediate enabled mechanistic investigations of this challenging bond cleavage process. This work substantiates the notion that terminal phosphinimide ligands can engender first-row transition metal ions with exceptional reactivity.

C-C Bond Cleavage Mediated Reaction for Constructing 3-Carbonyl Imidazo[1,5-a] Pyridines from 1,3-Dicarbonyl Compounds and Pyridin-2-ylmethanamines.

A [4 + 1] cyclization and C-C bond cleavage process mediated reaction for constructing 3-carbonyl imidazo[1,5-a] pyridines from 1,3-dicarbonyl compounds and pyridin-2-ylmethanamines has been developed. Various 1,3-dicarbonyl compounds are applicable, and selectivity could be achieved. Importantly, this strategy could be extended to an atom economy method by employing a cyclic 1,3-dicarbonyl compound, and it provided a new view for C-C bond cleavage reactions.

Four – Electron Oxidative Addition of an N=N Double Bond at a Chromium Metallocyclopropene

This report describes the synthesis of a pseudo‐tetrahedral chromium alkyne complex supported by a bidentate phosphinimide ligand and its reactivity with azobenzene. Characterization of the former by structural and computational methods reveals an unprecedented extent of alkyne activation by a formal chromium(II) center, suggesting that this complex is best described as a chromium(IV)‐metallocyclopropene. Exposure of this compound to an azobenzene derivative results in the formation of a chromium(VI) diimido complex, which constitutes a rare 4‐electron oxidative addition of an N=N double bond. The isolation of a chromium(IV)‐hydrazido intermediate enabled mechanistic investigations of this challenging bond cleavage process. This work substantiates the notion that terminal phosphinimide ligands can engender first‐row transition metal ions with exceptional reactivity.

E-H Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Hydrogen and p-Block Element Hydrides.

Reactions of complexes [MoMCp(μ-PMes*)(CO)6] with H2 and several p-block element (E) hydrides mostly resulted in the cleavage of E-H bonds under mild conditions [M = Re (1a) and Mn (1b); Mes* = 2,4,6-C6H2tBu3]. The reaction with H2 (ca. 4 atm) proceeded even at 295 K to give the hydrides [MoMCp(μ-H)(μ-PHMes*)(CO)6]. The same result was obtained in the reactions with H3SiPh and, for 1a, upon reduction with Na(Hg) followed by protonation of the resulting anion [MoReCp(μ-PHMes*)(CO)6]-. The latter reacted with [AuCl{P(p-tol)3}] to yield the related heterotrimetallic cluster [MoReAuCp(μ-PHMes*)(CO)6{P(p-tol)3}]. The reaction of 1a with thiophenol gave the thiolate-bridged complex [MoReCp(μ-PHMes*)(μ-SPh)(CO)6], which evolved readily to the pentacarbonyl derivative [MoReCp(μ-PHMes*)(μ-SPh)(CO)5]. In contrast, no P-H bond cleavage was observed in reactions of complexes 1a,b with PHCy2, which just yielded the substituted derivatives [MoMCp(μ-PMes*)(CO)5(PHCy2)]. Reactions with HSnPh3 again resulted in E-H bond cleavage, but now with the stannyl group terminally bound to M, while 1a reacted with BH3·PPh3 to give the hydride-bridged derivatives [MoReCp(μ-H)(μ-PHMes*)(CO)5(PPh3)] and [MoReCp(μ-H){μ-P(CH2CMe2)C6H2tBu2}(CO)5(PPh3)], which follow from hydrogenation, C-H cleavage, and CO/PPh3 substitution steps. Density functional theory calculations on the PPh-bridged analogue of 1a revealed that hydrogenation likely proceeds through the addition of H2 to the Mo=P double bond of the complex, followed by rearrangement of the Mo fragment to drive the resulting terminal hydride into a bridging position.

Photoinduced Biomimetic Room-Temperature C-O Bond Cleavage over Mn Doped CdS.

Selective C-O bond cleavage is an efficient way for the biomass valorization to value-added chemicals, but is challenged to be operated at room temperature via conventional thermal catalysis. Herein, inspired from the DNA biosynthesis which involves a radical-mediated spin-center shift (SCS) C-O bond cleavage process, we report a biomimetic room-temperature C-O bond cleavage of vicinal diol (HOCHCH-OH). We construct a Mn doped CdS (Mn/CdS) as a photocatalyst to mimic the biologic SCS process. The Mn site plays pivotal role: (1) accelerates the photo-induced carrier separation, promoting the hole-mediated C-H bond cleavage to generate carbon-centered radicals, and (2) serves as the binding site for -OH groups, making it to be an easier leaving group. Mn/CdS achieves 0.28 mmol gcat -1 h-1 of hydroxyacetone (HA) from glycerol dehydration at room temperature under visible light irradiation, which is 3.5-fold that over pristine CdS and 40-fold that over bulk MnS/CdS. This study provides a new biomimetic room-temperature C-O bond cleavage process, which is promising for the biomass valorization.

Cycloaddition and C-S Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Alkynes and Phenyl Isothiocyanate.

Reactions of [MoReCp(μ-PMes*)(CO)6] with internal alkynes RC≡CR yielded the phosphapropenylidene-bridged complexes [MoReCp(μ-κ2P,C:η3-PMes*CRCR)(CO)5] (Mes* = 2,4,6-C6H2tBu3; R = CO2Me, Ph). Terminal alkynes HC≡CR1 gave mixtures of isomers [MoReCp(μ-κ2P,C:η3-PMes*CHCR1)(CO)5] and [MoReCp(μ-κ2P,C:η3-PMes*CR1CH)(CO)5], with the first isomer being major (R1 = CO2Me) or unique (R1 = tBu), indicating the relevance of steric repulsions during the [2 + 2] cycloaddition step between Mo=P and C≡C bonds in these reactions. Similar reactions were observed for [MoMnCp(μ-PMes*)(CO)6]. Addition of ligands to these complexes promoted rearrangement of the phosphapropenylidene ligand into the allyl-like μ-η3:κ1C mode, as shown by the reaction of [MoReCp(μ-κ2P,C:η3-PMes*CHC(CO2Me)}(CO)5] with CN(p-C6H4OMe) to give [MoReCp{μ-η3:κ1C-PMes*CHC(CO2Me)}(CO)5{CN(p-CH4OMe)}2]. The MoRe phosphinidene complex reacted with S=C=NPh to give as major products the phosphametallacyclic complex [MoReCp{μ-κ2P,S:κ2P,S-PMes*C(NPh)S}(CO)5] and its thiophosphinidene-bridged isomer [MoReCp(μ-η2:κ1S-SPMes*)(CO)5(CNPh)]. The first product follows from a [2 + 2] cycloaddition between Mo=P and C=S bonds, with specific formation of P-C bonds, whereas the second one would arise from the alternative cycloaddition involving the formation of P-S bonds, more favored on steric grounds. The prevalence of the μ-η2:κ1S coordination mode of the SPMes* ligand over the μ-η2:κ1p mode was investigated theoretically to conclude that steric congestion favors the first mode, while the kinetic barrier for interconversion between isomers is low in any case.

Autoionization from the plasmon resonance in isolated 1-cyanonaphthalene.

Polycyclic aromatic hydrocarbons have widely been conjectured to be ubiquitous in space, as supported by the recent discovery of two isomers of cyanonaphthalene, indene, and 2-cyanoindene in the Taurus molecular cloud-1 using radioastronomy. Here, the photoionization dynamics of 1-cyanonaphthalene (1-CNN) are investigated using synchrotron radiation over the hν = 9.0-19.5eV range, revealing that prompt autoionization from the plasmon resonance dominates the photophysics for hν = 11.5-16.0eV. Minimal photo-induced dissociation, whether originating from an excited state impulsive bond rupture or through internal conversion followed by a statistical bond cleavage process, occurs over the microsecond timescale (as limited by the experimental setup). The direct photoionization cross section and photoelectron angular distributions are simulated using an ezDyson model combining Dyson orbitals with Coulomb wave photoejection. When considering these data in conjunction with recent radiative cooling measurements on 1-CNN+, which showed that cations formed with up to 5eV of internal energy efficiently stabilize through recurrent fluorescence, we conclude that the organic backbone of 1-CNN is resilient to photodestruction by VUV and soft XUV radiation. These dynamics may prove to be a common feature for the survival of small polycyclic aromatic hydrocarbons in space, provided that the cations have a suitable electronic structure to support recurrent fluorescence.

Active Site Identification for Glycerol Hydrodeoxygenation over the Oxygen Modified Molybdenum Carbide Surface

Density functional theory and microkinetic reactor modeling were used to investigate the hydrodeoxygenation (HDO) mechanism of glycerol on the oxygenated Mo2C catalyst surface to understand the activity and product selectivity under practically relevant reaction conditions. Reactor simulations with multiple active site models predicted that a fully oxygenated surface with acid–base (OH,O) pairs is active for glycerol dehydration and it can selectively cleave one C–O bond to produce 3-hydroxypropanal (HPA). The acid sites are not directly involved in the C–O bond scission process; however, surface oxygen vacancy formation is promoted in the presence of acid sites. The rate-limiting C–O bond cleavage process occurs on the exposed Mo sites with a concerted β-hydrogen transfer to the nearest conjugate base (Mo–O) via an E2 elimination mechanism. Dehydration of HPA to acrolein was observed at longer residence times. Our analysis revealed that reaction conditions, such as temperature and partial pressure of H2, can be tuned to promote further deoxygenation of HPA and acrolein to produce propanal and propylene.

A novel ZnO/CQDs/PVDF piezoelectric system for efficiently degradation of antibiotics by using water flow energy in pipeline: Performance and mechanism

Using clean and natural energy from the environment to treatment of organic pollutants is a sustainable approach to alleviate energy and environmental problem. This work prepared a novel ZnO/CQDs/PVDF pipe system with excellent piezoelectric properties for efficient tetracycline (TC) degradation. The piezoelectric catalytic activity of ZnO/CQDs/PVDF was excited by hydrodynamic force to achieve a removal rate of 95.17 % of TC within 70 min with a second-order kinetic constant of 0.0185 L∙(mg min)−1, it can still maintain high stability after 35 h cycles. Most importantly, the water flow-driven piezoelectric catalytic system has extremely low energy consumption, is only 17.57 % of that of the ultrasonic system. The CQDs promote the transfer rate of ZnO surfaces charges, and PVDF with flexible β-rich phases were more sensitive to low-frequency pressure responses. ∙OH and ∙O2- radicals were demonstrated to the main radicals for the degradation of tetracycline. Based on LC-MS results and DFT calculations, the degradation mechanisms of tetracycline molecules, including hydroxylation, C-C, and C-N bond cleavage processes, were successfully predicted. In addition, ZnO/CQDs/PVDF pipe have obvious inhibitory effect on the biotoxicity of intermediates generated during the degradation process and exhibit excellent antibacterial ability. This work demonstrated that ZnO/CQDs/PVDF pipe have efficient utilization of low-frequency water flow energy and shows great potential in practical applications.

Silyl Tether-Assisted Photooxygenation of Electron-Deficient Enaminoesters: Direct Access to Oxamate Formation.

Photooxygenation reactions of electron-deficient enaminoesters bearing an oxophilic silyl tether at the α-position of the nitrogen atom using methylene blue (MB) were explored to develop a mild and efficient photochemical strategy for oxidative C-C double bond cleavage reactions via singlet oxygen (1O2). Photochemically generated 1O2, through energy transfer from the triplet excited state of MB (3MB*) to molecular oxygen (3O2), was added across a C-C double bond moiety of enaminoesters to form perepoxides, which rearranged to form dioxetane intermediates. The cycloreversion of the formed dioxetane via both C-C and O-O bond cleavage processes led to the formation of oxamates. Importantly, contrary to alkyl group tether-substituted electron-deficient enaminoesters that typically disfavor photooxygenation, the silyl tether-substituted analogues undergo this photochemical transformation efficiently with the assistance of a silyl tether, which facilitates formation of the perepoxide. The observations in this study provide useful information about photosensitized oxygenation reactions of unsaturated C-C bonds, and, moreover, this photochemical strategy can be utilized as a mild and feasible method for the preparation of diversely functionalized carbonyl compounds including oxamates.

Synergistic Engineering of Doping and Vacancy in Ni(OH)2 to Boost Urea Electrooxidation

AbstractNickel hydroxide (Ni(OH)2) has been identified as one of the best promising electrocatalyst candidates for urea oxidation reaction (UOR) due to its flexible structures, wide compositions, and abundant 3d electrons under alkaline conditions. However, its layered structure with limited exposed edge sites severely hinders further improvement of the UOR activity. Herein, oxygen‐vacancy rich and vanadium doped Ni(OH)2 (Ovac‐V‐Ni(OH)2) catalysts are prepared and synergistically boost the urea electrooxidation. Vanadium doping contributes more exposed active sites, and simultaneously generates oxygen vacancies, switching the rate‐determining step of UOR from *COOH deprotonation to the N–H bond cleavage process and lowering the thermodynamic barrier by around 1.13 eV. The novel Ovac‐V‐Ni(OH)2 demonstrates good electrocatalytic performances with a working potential of 1.47 V at a high current density of 100 mA cm−2. Synergistic engineering of doping and oxygen vacancy is a promising strategy for designing efficient UOR electrocatalysts.

Rhodium-catalyzed aerobic conversion of 2-diazo-1,3-dicarbonyls to vicinal tricarbonyl compounds and their in-situ stability toward oxidative degradation

Several types of 2-diazo-1,3-dicarbonyl compounds (3), including α-diazo-β-ketoesters, 2-diazo-1,3-diketones and diazomalonates, are converted into the corresponding vicinal tricarbonyls (VTCs) (4) upon exposure to Rh2(OAc)4 catalyst and oxygen gas. The transformation is proposed to occur through the aerobic oxygenation of the rhodium carbenoid intermediate, facilitated by the suppression of a Wolff rearrangement via weak interaction with the substrate carbonyl group (ROC=O or RC=O). The reactions of α-diazo-β-ketoesters and 2-diazo-1,3-diketones give the desirable α,β-diketoesters and vic-triketones in 27-78% isolated yields, along with carboxylic acids and/or 2-oxoacids generated by in-situ oxidative C-C single bond cleavage of the former products. Moreover, the bond cleavage process is completely inhibited when the reactions are performed with diazomalonates, leading to the good to excellent formation of oxomalonates (up to 92% yield).

Insights into atrazine degradation by thermally activated persulfate: Evidence from dual C–H isotope analysis and DFT simulations

SO4– -assisted oxidation was of great concern and the accurate interpretation of reaction pathway was crucial. Innovatively, this study introduced compound-specific isotope fractionation analysis (CSIA) into atrazine (ATZ) degradation by heat-activated persulfate (PS), in order to provide “in-situ” and “fingerprinted” analysis of reaction contribution and bond cleavage process based on isotope fractionation. As results, radical oxidants including SO4- and OH were generated through thermal activation of PS, and proved to play dominate roles in ATZ degradation. Inconceivably, the isotope fractionation by single SO4-dominated reaction showed weak and positive C isotope fractionation, with εC of 1.58 ‰ at pH 4 and 0.65 ‰ at pH 7, respectively. Reactions by single SO4- and OH can be distinguished resulting from their significantly different ε and ɅC/H values. Changes of δ13C and δ2H values during ATZ degradation by heat-activated PS followed Rayleigh equation well, with the εC, εH and ɅC/H values of −1.5 ‰, −21.1 ‰, 6.60 at pH 4 and −2.7 ‰, −36.6 ‰, 10.02 at pH 7 respectively. The relative contribution of SO4- radical to ATZ degradation was ca.100 % at pH 4 and 83.9 % at pH 7. The isotope fractionation study and DFT calculations suggested that single electron transfer with the cleavage of C-Cl bond was dominated and displayed inverse C isotope fractionation for SO4- oxidation, which was different from that of OH oxidation and more selective to dehalogenate reaction. This research emphasized the promising technology of CSIA, which can achieve accurate identification of reaction contribution and pathways in advanced oxidation process.

B(C6F5)3-Catalyzed α,β-Difunctionalization and C-N Bond Cleavage of Saturated Amines with Benzo[c]isoxazoles: Access to Quinoline Derivatives.

Herein, we disclose a strategy to realize α,β-difunctionalization and C-N bond cleavage of saturated amines with benzo[c]isoxazoles via a B(C6F5)3-catalyzed consecutive hydrogen-borrowing and [4 + 2] cycloaddition followed by a C-N bond cleavage process. In general, the reactions proceed efficiently in the absence of any oxidant and metal catalyst to afford a broad range of quinoline derivatives starting from easily accessible substrates in an atom-economical manner.