Divergent defluorocarboxylation of α-CF_(3) alkenes with formate via photocatalyzed selective mono-or triple C-F bond cleavage

Unprecedented divergent synthesis of gem-difluorovinylacetic acid and glutaric acid derivatives fromα-CF_(3)alkenes with formate as the carbonyl source was disclosed.The reaction can undergo selective mono-or triple C-F bond cleavage by simply switching the photocatalyst and hydrogen atom transfer(HAT)catalyst under visible-light-induced conditions at room temperature.Foramte acts as both the C1 source and the reductant through the generation of CO_(2)^(·-)species,which underwent Giese radical addition to electron-deficient alkenes to trigger the consecutive C-F bond cleavage and carboxylation process.

Biomass valorization via electrocatalytic carbon–carbon bond cleavage

Renewable electrocatalytic upgrading of biomass feedstocks into valuable chemicals is one of the promising strategies to relieve the pressure of traditional energy-based systems.Through electrocatalytic carbon–carbon bond cleavage of high selectivity,various functionalized molecules,such as organic acids,amides,esters,and nitriles,have great potential to be accessed from biomass.However,it has merely received finite concerns and interests in the biorefinery.This review first showcases the research progress on the electrocatalytic conversion of lipid/sugar-and lignin-derived molecules(e.g.,glycerol,mesoerythritol,xylose,glucose,1-phenylethanol,and cyclohexanol)into organic acids via specific carbon–carbon bond scission processes,with focus on disclosing reaction mechanisms,recognizing actual active species,and collecting feasible modification strategies.For the guidance of further extensive studies on biomass valorization,organic transformations via a variety of reactions,including decarboxylation,ring-opening,rearrangement,reductive hydrogenation,and carboxylation,are also disclosed for the construction of similar carbon skeletons/scaffolds.The remaining challenges,prospective applications,and future objectives in terms of biomass conversion are also proposed.This review is expected to provide references to develop renewed electrocatalytic carbon–carbon bond cleavage transformation paths/strategies for biomass upgrading.

Mineral cleavage nature and surface energy: Anisotropic surface broken bonds consideration

The population of surface broken bonds of some typical sulfide, oxide and salt-type minerals which may belong to cubic, tetragonal, hexagonal, or orthorhombic system, were calculated. In terms of the calculation results, the cleavage natures of these minerals were analyzed, and the relationship between surface broken bonds density and surface energy was also established. The results show that the surface broken bonds properties could be used to predict the cleavage nature of most of minerals, and the predicted cleavage planes agree well with those reported in previous literature. Moreover, this work explored a rule that, surface broken bonds density is directly related to surface energy with determination coefficient（R2） of over 0.8, indicating that the former is a dominant factor to determine the latter. Therefore, anisotropic surface broken bonds density can be used to predict the stability of mineral surface and the reactivity of surface atoms.

Hydroxyl radicals-mediated oxidative cleavage of the glycosidic bond in cellobiose by copper catalysts and its application to low-temperature depolymerization of cellulose

As the most abundant source of biomass in nature for sustainable production of fuels and chemicals,efficient depolymerization of cellulose under mild conditions,due to the difficulty in selective cleavage of itsβ-1,4-glycosidic bonds,still remains challenging.Here,we report a novel method for oxidative cleavage of the glycosidic bonds by free radicals.Probed by the cellobiose reaction,it was found that·OH radicals,generated from the decomposition of H2O2 catalyzed by CuSO4 or CuO/SiO2,were efficient for selective conversion of cellobiose to glucose and gluconic acid at a low temperature of 333 K,and their selectivities reached 30.0%and 34.6%,respectively,at 23.4%cellobiose conversion.Other radicals,such as·SO4?,also exhibited high efficacy in the cellobiose reaction.Mechanistic studies suggest that the oxidative cleavage of theβ-1,4-glycosidic bond by the free radicals involve formation of the carbon radical intermediate via abstraction of the H atom dominantly at the C1 position.Following this oxidative mechanism,treatment of microcrystalline cellulose with·OH by impregnation with H2O2 and CuSO4 catalyst at 343 K led to significant enhancement in its hydrolysis efficiency.These results demonstrate the effectiveness of this new method in the oxidative cleavage of glycosidic bonds,and its viability for the efficient depolymerization of cellulose at low temperatures,which can be further improved,for example,by exploring new free radicals and optimizing their reactivity and selectivity.

Ni-catalyzed carbon–carbon bonds cleavage of mixed polyolefin plastics waste

The inert carbon–carbon(C–C) bonds cleavage is a main bottleneck in the chemical upcycling of recalcitrant polyolefin plastics waste. Here we develop an efficient strategy to catalyze the complete cleavage of C–C bonds in mixed polyolefin plastics over non-noble metal catalysts under mild conditions. The nickelbased catalyst involving Ni_(2)Al_(3) phase enables the direct transformation of mixed polyolefin plastics into natural gas, and the gas carbon yield reaches up to 89.6%. Reaction pathway investigation reveals that natural gas comes from the stepwise catalytic cleavage of C–C bonds in polypropylene, and the catalyst prefers catalytic cleavage of terminal C–C bond in the side-chain with the low energy barrier.Additionally, our developed approach is evaluated by the technical economic analysis for an economically competitive production process.

Studies on a New Usage of Hypophosphorous Acid-iodine System in N-C Bond Cleavage

A mixture of hypophosphorous acid (H3PO2) and iodine in acetic acid can cleave the N-alkyl bond in a variety of N-1 substituted pyrimidine derivative in relatively high yields, without any damage to the amido bond in the non-nucleosides pyrimidine base skeleton.

Structural and electronic effects boosting Ni-doped Mo_(2)C catalyst toward high-efficiency C-O/C-C bonds cleavage

The selective cleavage of C-O and C-C is facing a challenge in the field of catalysis.In the present work,we studied the influence of doped Ni on the structure and electronic properties,as well as the selective C-O/C-C bond cleavages in the hydrodeoxygenation of palmitic acid over Ni-Mo_(2)C catalyst.The catalytic activity on Ni doped Mo_(2)C with TOF of 6.9×10^(3)h^(-1)is much superior to intrinsic Mo_(2)C catalyst,which is also higher than most noble metal catalysts.Structurally,the doped Ni raises the active particle dispersion and the coordination numbers of Mo species(Mo-C and Mo-O),improves the graphitization degree to promote the electron transfer,and increases the amount of Lewis and Br?nsted acid,which are responsible for the excellent hydrodeoxygenation performance.The Ni promotes simultaneously C-O and C-C bonds cleavage to produce pentadecane and hexadecane owing to the increase of electron-rich Mo sites after Ni doping.These findings contribute to the understanding of the nature of Ni-doped Mo_(2)C on the roles as catalytic active sites for C-O and C-C bonds cleavage.

COPE REARRANGEMENT INVOLVING CARBON—CARBON BOND CLEAVAGE

A new type of Cope rearrangement involving carbon-carbon bond cleavage (or de-tbutylation) was found during the heating of 4-allyl-4-methyl-2, 6-di-t-butylsemiquinone,

The Preparation of Unsymmetrical Diaminodimethylsilanes and the Cleavage of Silicon-Nitrogen Bonds by Acid Chloride

Seven unsymmetrical diaminodimethylsilanes were prepared. The reactions of these silylamine with benzoyl chloride indicated that in comparison with electronic, the steric effect played more important role on the reactivity of Si-N bond. As a new method, unsymmetrical diamide can produced by the reaction of the title compounds with diacid chloride.

β-Cyclodextrin Facilitates the Cleavage of Cobalt-Carbon Bonds during the Electrochemical Reduction of Alkylaquabis(dimethylglyoximato)Cobalt(Ⅲ)

The electrochemical reduction of alkylaquabis (dimethylglyoximato)Cobalt(Ⅲ) in the absence and presence of β-Cyclodextrin (β-CD) was inveingated by means of cylic voltammetry. It was found that β-CD facilitates the cleavage of Co-C bond during the reduchon process.

Copper-Catalyzed C-C(O)C Bond Cleavage of Monoalkylated β-Diketone: Synthesis of α,β-Unsaturated Ketones

A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K3PO4) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .

Synthesis, Characterization and Crystal Structure of a New Schiff Base Ligand from a Bis(Thiazoline) Template and Hydrolytic Cleavage of the Imine Bond Induced by a Co(II) Cation

The reaction of bis-[2-amino-4-pheny1-5-thiazolyl] disulfide with 5-nitro-salicylaldehyde in absolute ethanol resulted in the formation of a new Schiff base ligand H2L (1). Characterization of the ligand was performed by FT-IR, 1H NMR, 13C NMR, UV-Vis, elemental analysis and single crystal X-ray diffraction. The ligand, (1), possesses a disulfide –S–S– bridge of 2.1121 (3) ? length, and the molecule adopts a cis-conformation around this bond. In the crystal structure of (1), an intramolecular O–H···N hydrogen bond with D… A distance of 2.69 (3) ? was present. The reaction of (1) with Co(NO3)2·6H2O and CuCl2·2H2O in methanol afforded the corresponding metal complexes. The obtained solids were further investigated by elemental analysis and UV-Vis titration that confirmed the formation of [CoL] and [ClCuHL] complexes. However, recrystallizaion of the Co(II) complex in dimethylsulfoxide caused the complete hydrolysis of the imine bond and afforded a Co(II) complex in which two 5-nitro-salicylaldehyde and two DMSO molecules were coordinated to the central metal in an octahedral fashion. This structure (2) was also confirmed by single crystal X-ray analysis.

Density Functional Studies of the Reaction of Ytterbium Monocation with Fluoromethane:C-F Bond Activation and Electron-Transfer Reactivity

The potential energy surface and reaction mechanism corresponding to the reaction of ytterbium monocation with fluoromethane, which represents a prototype of the activation of C-F bond in fluorohydrocarbons by bare lanthanide cations, have been investigated for the first time by using density functional theory. A direct fluorine abstraction mechanism was revealed, and the related thermochemistry data were determined. The electron-transfer reactivity of the reaction was analyzed using the two-state model, and a strongly avoided crossing behavior on the transition state region was shown. The present results support the reaction mechanism inferred from early experimental data and the related thermochemistry data can provide a guide for further experimental researches.

Cooperative catalysis of Co single atoms and nanoparticles enables selective CAr-OCH_(3) cleavage for sustainable production of lignin-based cyclohexanols

In this work,a dual-size MOF-derived Co catalyst(0.2Co_(1-NPs)@NC)composed of single atoms(Co_(1))and highly dispersed nanoparticles(Co NPs)was prepared by in-situ Zn evaporation for the highperformance conversion of lignin-derived o-methoxyphenols(lignin oil)to cyclohexanols(up to 97%yield)via cascade demethoxylation and dearomatization.Theoretical calculations elaborated that the dual-size Co catalyst exhibited a cooperative effect in the selective demethoxylation process,in which the Co NPs could initially dissociate hydrogen at lower energies while Co1remarkably facilitated the cleavage of the C_(Ar)-OCH_(3)bond.Moreover,the intramolecular hydrogen bonds formed in the omethoxy-containing phenols were found to result in a decrease in the bond energy of the C_(Ar)-OCH_(3)bond,which was more prone to be activated by the dual-size Co sites.Notably,the pre-hydrogenated intermediate(e.g.,2-methoxycyclohexanol from guaiacol)is difficult to undergo demethoxylation,indicating that the selective C_(Ar)-OCH_(3)bond cleavage is a prerequisite for the synthesis of cyclohexanols.The 0.2Co_(1-NPs)@NC catalyst was highly recyclable with a neglect decline in activity during five consecutive cycles.This cooperative catalytic strategy based on the metal size effect opens new avenues for biomass upgrading via enhanced C-O bond cleavage of high selectivity.

Anisotropic surface broken bond properties and wettability of calcite and fluorite crystals

Anisotropic surface broken bond densities of six different surfaces of calcite and three surfaces of fluorite were calculated. In terms of the calculated results, the commonly exposed surfaces of the two minerals were predicted and the relations between surface broken bonds densities and surface energies were analyzed. Then the anisotropic wettability of the commonly exposed surfaces was studied by means of contact angle measurement. The calculation results show that the （101^-4）, （213^-4）and （01 1^-8）surfaces for calcite and （111） for fluorite are the most commonly exposed surfaces and there is a good rectilinear relation between surface broken bond density and surface energy with correlation of determination （R^2） of 0.9613 and 0.9969, respectively. The anisotropic wettability of different surfaces after immersing in distilled water and sodium oleate solutions at different concentrations can be explained by anisotropic surface broken bond densities and active Ca sites densities, respectively.

Copper-Mediated Selective Multiple Inert Chemical Bonds Cleavage for Cyanation of Indoles via Tandem Carbon and Nitrogen Atom Transfer

Comprehensive Summary The activation of inert chemical bonds is an exciting area of research in chemistry because it enables the direct utilization of readily available starting materials and promotes atom-and step-economic synthesis.Undoubtedly,selectively activating and transforming multiple inert chemical bonds is an even more intriguing and demanding task in synthetic chemistry.However,due to its inherent complexity and extreme challenges,this endeavour is rarely accomplished.We report a copper-mediated complete cleavage and selective transformation of multiple inert chemical bonds of three easily available feedstocks,i.e.,a sp2C—H bond in indoles,three sp3C—H bonds and one C—N bond in a methyl carbon atom in TMEDA,and the C≡N triple bond in CH_(3)CN.This reaction proceeds via tandem carbon and nitrogen atom transfer,and allows for the direct and efficient cyanation of indoles,presenting a simple and direct alternative for synthesizing 3-cyanoindoles.

Regioselective C-C bond cleavage/aminocarbonylation cascade under copper catalysis

A regioselective C-C bond cleavage/aminocarbonylation cascade is presented. In recent years, tremendous progress has been made in the alkoxyl radical-mediated C-C bond cleavage of unstrained monocarbocycles. In contrast, the deconstruction and functionalization of bicyclic skeletons has been less developed and has mainly focused on the ring expansion process. Inspired by the aromatization-driven C-C bond cleavage, here we demonstrate a ring-opening/aminocarbonylation cascade under copper catalysis, in which the formation of a stable γ-lactam or succinimide skeleton reverses the selectivity of C-C cleavage. Remarkably, the photo and thermal assistance is not required when the succinimide skeleton is formed during the ring opening process. DFT calculations revealed that this unexpected ring-opening process is thermodynamically and kinetically favourable.

Clean production of lactic acid by selective carbon-carbon bond cleavage of biomass feedstock over a novel carbon-bismuth oxychloride photocatalyst

The use of functional materials such as carbon-bismuth oxyhalides in integrated photorefineries for the clean production of fine chemicals requires restructuring.A facile biomass-assisted solvothermal fabrication of carbon/bismuth oxychloride nanocomposites(C/BiOCl)was achieved at various temperatures.Compared with BiOCl and C/BiOCl-120,C/BiOCl-180 exhibited higher crystallinity,wider visible light absorption,and a faster migration/separation rate of photoinduced carriers.For the selective C–C bond cleavage of biomass-based feedstocks photocatalyzed by C/BiOCl-180,the xylose conversion and lactic acid yield were 100%and 92.5%,respectively.C/BiOCl-180 efficiently converted different biomass-based monosaccharides to lactic acid,and the efficiency of pentoses was higher than that of hexoses.Moreover,lactic acid synthesis was favored by all active radicals including superoxide ion(·O_(2)^(−)),holes(h^(+)),hydroxyl radical(·OH),and singlet oxygen(^(1)O_(2)),with·O_(2)^(−)playing a key role.The fabricated photocatalyst was stable,economical,and recyclable.The use of biomass-derived monosaccharides for the clean production of lactic acid via the C/BiOCl-180 photocatalyst has opened new research horizons for the investigation and application of C–C bond cleavage in biomass-based feedstocks.

Enhancement of CH_(3)CO^(*) adsorption by editing d-orbital states of Pd to boost C–C bond cleavage of ethanol eletrooxidation

Improving the complete ethanol electrooxidation on Pd-based catalysts in alkaline media has drawn widely attention due to the high mass energy density.However,the weak adsorption energy of CH_(3)CO^(*) on Pd restricts the C–C bond cleavage.Inspired by the molecular orbital theory,we proposed the d-state-editing strategy to construct more unoccupied d-states of Pd for the enhanced interaction with CH_(3)CO^(*) to break C–C bonds.As expected,the reduced number of e_g electrons and more unoccupied d-states of Pd successfully formed on as-prepared porous Rh Au–Pd Cu nanosheets(PNSs).Theoretical calculations show that the optimized d-states of Rh Au–Pd Cu PNS can effectively improve the adsorption of CH_(3)CO^(*) and drastically reduce the energy barrier of C–C bond cleavage,thus boosting the complete oxidation of ethanol.The charge ratio of C_1 pathway on Rh Au–Pd Cu PNSs is 51.5%,more than 2 times higher than that of Pd NSs.Our finding provides an innovative perspective for the design of highly-efficient noble-based electrocatalysts.

矿物解理/断裂规律与晶面间距的弱相关性及证明

应用密度泛函理论、断裂键理论和晶体化学性质,定量研究了矿物解理/断裂的晶体化学机制以及与晶面间距(或面网间距)的关系。归纳发现,矿物常见解理/断裂面并不总是与晶面间距最大的晶面相对应,体现为弱相关性。理论计算结果表明,矿物常见解理/断裂面对应于表面能最低的晶面,而表面能与面网密度及晶面原子平均断裂键数τ正相关。晶面间距与面网密度正相关,意味着当晶面间距大的晶面成为常见解理/断裂面时,需通过降低晶面原子平均断裂键数τ值以降低表面能。然而,通过分析发现,晶面间距与晶面原子平均断裂键数τ的关联性差,从而使得晶面间距与矿物解理/断裂规律无直接关联性。本文的研究结果能够为矿物解理/断裂规律以及表面性质研究提供理论借鉴。