37 results about "Photoredox catalysis" patented technology

The invention relates to the fields of medicine, organic chemical industry and fine chemical industry, in particular to a method for synthesizing 1, 4-diketone by catalyzing alkenyl amide and alpha-carbonyl oxidized sulfonium ylide through photooxidation reduction. The preparation method comprises the following steps: under the protection of inert gas, reacting alkenyl amide and alpha-carbonyl oxidized sulfonium ylide serving as substrates in an organic solvent by taking a photosensitizer as a catalyst under the action of blue light irradiation and alkali at 30 DEG C for 18 hours to obtain an alkenyl amide alpha-carbonyl alkylate, and then hydrolyzing under an acidic condition to synthesize various asymmetric 1, 4-diketone compounds. The 1, 4-diketone compound is synthesized by a two-step method by taking alkenyl amide and alpha-carbonyl oxidized sulfonium ylide as initial raw materials, and the method has the remarkable advantages of wide substrate raw material sources, simplicity and convenience in operation, mild reaction conditions, high reaction efficiency, good universality, excellent functional group compatibility and the like.

The present disclosure provides compositions and methods for metathesizing a first alkenyl or alkynyl group with a second alkenyl or alkynyl group, the composition comprising a ruthenium metathesis catalyst and a photoredox catalyst that is activated by visible light.

The invention discloses a method for photocatalytic synthesis of N, O-spiroketal amine derivatives, and belongs to the technical field of organic synthesis. Aiming at the problems of harsh conditions, small substrate range and the like of the existing synthesis method, the invention provides the method for photocatalytic synthesis of the N, O-spiroketal amine derivative, and the method comprises the following steps: mixing a 1-alkenyloxy ring compound, a 1-azido vinyl ring compound, a photocatalyst, alkali and an organic solvent, and carrying out photocatalytic reaction to obtain the N, O-spiroketal amine derivative. The 1, 1, 2-trifunctional reaction of the N-alkenyloxy onium salt and the vinyl azide is successfully realized through a strategy of efficiently constructing an N, O-spiroketal amine skeleton under the catalysis of photooxidation reduction, and the method is simple and convenient to operate and high in yield. The method is mild in reaction condition, stable in process condition, high in product yield, easy in product purification, wide in substrate range, good in functional group tolerance, low in production cost and suitable for large-scale production.

This invention discloses a migration C(sp²)-H / C(sp³)-H cross-coupling reaction achieved using metal / photoredox catalysis, belonging to the fields of organic chemistry and medicinal chemistry. Under the action of a nickel source, photocatalyst, ligands, base, and additives, this invention enables the reaction of alkanes with ortho-alkenyl-substituted aryl halides or ortho-pyridine-substituted aryl halides in an organic solvent under light irradiation, yielding a series of polysubstituted olefins or polysubstituted aromatic compounds with excellent regioselectivity, stereoselectivity, and good yields, which can serve as active pharmaceutical molecules. This invention uses inexpensive transition metal nickel as a catalyst, readily available alkanes and haloaromatics as raw materials, and features mild and simple conditions, good functional group compatibility, and easy operation.

The invention relates to the technical field of organosilicon chemistry, in particular to a preparation method of a phenyltrimethoxysilane oligomer. According to the method, a photooxidation reduction catalytic system is adopted, a hydrolytic condensation reaction is carried out under the irradiation of visible light, the ratio of M / T substance amount is controlled, a proton coupling electron transfer mechanism is adopted to activate silane bonds, and an acid-base catalyst does not need to be additionally added. Efficient synthesis is realized in a continuous flow microchannel reactor by introducing innovative components such as a cyanoalkyl silane end-capping reagent, an organic titanium prepolymer catalyst and polyhedral oligomeric silsesquioxane. The obtained oligomer has a controllable molecular structure and excellent performance, the methoxy residual quantity is lower than 0.3%, the yield reaches 90% or above, the viscosity is controlled to be 18-25 mm < 2 > / s, the refractive index is 1.460-1.465, and the oligomer has the reversible crosslinking characteristic and is suitable for high-end cosmetics and electronic packaging materials.

The synthesis method comprises the following steps: synthesizing an organic compound containing an alkenyl silicon skeleton by taking silaborane as a silicon free radical precursor, aryl bromide as a coupling component and morpholine as an accelerant and adopting a photooxidation reduction / nickel dual-catalysis system; according to the method, photo-oxidation reduction catalysis and nickel catalysis are combined, challenging alkenyl silicon bonds and carbon-carbon bonds are effectively constructed, conversion which is difficult to complete through a traditional method is achieved, the problems that a traditional transition metal catalytic catalyst is expensive and poor in selectivity are solved, and the method has the advantages of being mild, environmentally friendly, high in reaction efficiency and the like.

The application discloses a synthesis method of aromatic aldehyde, comprising the following steps: under inert atmosphere, a compound shown in formula I and a compound shown in formula II are reacted in an organic solvent containing a photocatalyst, a nickel catalyst, a ligand, a base and water under blue light irradiation to obtain aromatic aldehyde shown in formula III; formula I, formula II and formula III are structures as follows, ring A is selected from benzene, pyridine, thiophene, furan, pyridazine, indazole, indole, isoquinoline, quinoline, naphthalene, benzothiophene, dibenzofuran or dibenzothiophene; the application generates formyl radicals under the nickel synergistic photo-oxidation and reduction catalytic condition, and the formylation of bromobenzene and its derivatives is realized in a simple and efficient one-pot way, aromatic aldehyde is constructed, and the reaction has the characteristics of cheap and easily available raw materials, mild reaction conditions, controllable synthesis process, high separation yield / yield, green environmental protection, wide substrate applicability and the like.

A dental adhesive composition containing a polymerizable monomer (A) having an acidic group and a photoredox catalyst (B) having a singlet excited state reduction potential ES1red of 1.5 V vs SCE or more.

The invention relates to the fields of medicine, organic chemical industry and fine chemical industry, and particularly discloses a method for synthesizing a perfluoropyridine substituted glycine derivative through photooxidation reduction catalysis. According to the method, an N-arylglycine derivative and perfluoropyridine are taken as initial raw materials, and various alpha-(perfluoro-4-pyridine) phenylglycine derivatives and N-(perfluoro-4-pyridyl) phenylglycine derivatives can be efficiently synthesized under the condition that visible light and a photosensitizer participate in catalysis. Accurate regulation and control of reaction region selectivity are realized by regulating and controlling the type and proportion of the additive alkali, and alpha-C (sp3)-H and N-H substituted polyfluoro heteroarylation products are respectively obtained. The method has the advantages of mild reaction conditions, no metal participation, no need of additional oxidant, high reaction yield and the like. In addition, the method is simple to operate, excellent in regioselectivity and good in substrate functional group compatibility, and a new thought can be provided for polyfluorinated heteroarylation modification of amino acid.

The present invention discloses an oxygen-resistant photo-redox catalytically triggered ONOO ‑ The invention relates to the field of photoredox catalysis technology. The invention adopts amphiphilic block polymer and photocatalyst molecules to self-assemble to prepare nanoassemblies. The photocatalyst molecules in the nanoassemblies can act as photoredox catalysts to activate NO donor molecules in the amphiphilic block polymer to release NO under light conditions, and can also act as type I photosensitizers to generate O2 under light conditions. ·‑ , while NO and O2 ·‑ Further reaction produces ONOO ‑ , used to kill Gram-positive / negative bacteria, fungi and resistant Gram-negative bacteria.

The application provides a kind of intracellular near-infrared light catalysis nano-assembly and preparation method and application, the nano-assembly of the application involves three components, one is the photocatalyst with near-infrared absorption, simultaneously as photothermal reagent, two is NO release base element, three is amphiphilic block copolymer polyethylene glycol block polycaprolactone.By fast nano precipitation method, amphiphilic block copolymer is self-assembled in aqueous solution to load photocatalyst and NO release base element, obtain nano-assembly, the photocatalyst molecule in the nano-assembly can be used as photo-oxidation and reduction catalyst under light condition to activate NO donor molecule to release NO, can also consume intracellular NADH, can also produce heat, can effectively kill triple-negative breast cancer tumor cells, and effectively inhibit tumor growth in mouse subcutaneous tumor model.

Positron emission tomography and magnetic resonance imaging are among the most widely used modalities, requiring isotopic labeling of bioactive molecules to generate the desired imaging probes. This method was applied to a wide range of aliphatic carboxylic acids, including complex and functionalized drug molecules, amino acids and short peptides. For non-stabilized radicals derived from benzylic and non-benzylic carboxylic acids, a copper co-catalyst was introduced to obtain the labeled nitriles, whereas metal-free conditions were applied to nitrogen-stabilized radical derived from a-amino acids and peptides to form the radiolabeled a-amino nitriles. These radiolabeled nitriles were then easily converted back to radiolabeled carboxylic acids.

A method for the synthesis of two-dimensional (2D) bismuth (bismuthene) and a use of this material as a photoredox catalyst are provided. The 2D bismuthene is prepared by a liquid-phase exfoliation of the 3D-layered bismuth. The photoredox catalyst is used for the C-H functionalization reactions for the synthesis of complex molecules under versatile conditions.

The present invention relates to a light-curing, reactive, pressure-sensitive adhesive film of adhesive. With the film of adhesive of the invention, structural bond strengths can be achieved. The film of adhesive comprises (a) at least one reactive monomer or reactive resin, (b) an initiator, (c) a photoredox catalyst, (d) a polymer of monomers comprising N-vinyl compounds and (e) a film-forming polymer.

The invention discloses a method for constructing an aza-arene alpha-chiral center through asymmetric photooxidation reduction catalysis, and belongs to the field of organic synthesis.The preparation process specifically comprises the steps that under the protective atmosphere, cyano aza-arene shown in the formula I, Hanss ester 1, 4-dihydropyridine shown in the formula II and alpha-borate-alpha-substituted olefin shown in the formula III are subjected to a reaction at the temperature of 50-60 DEG C, and the aza-arene alpha-chiral center is obtained. In a solvent, DPZ is used as a visible light oxidation reduction catalyst, L-tertiary leucine-derived bisamide (C1) is used as a procedure catalyst, stirring reaction is performed completely at room temperature under visible light irradiation, and separation and purification are performed to obtain the target aza-arene alpha-chiral center derivative IV. According to the present invention, the high enantioselectivity is achieved, and the wide practicality in the efficient construction of the deuterium-labeled tertiary carbon stereo center with the pharmaceutical attraction is represented; in general, the method provides a simple, efficient and practical strategy for enantioselective synthesis of high-value aza-aromatic alpha-chiral center derivatives.

Positron emission tomography and magnetic resonance imaging are among the most widely used modalities, requiring isotopic labeling of bioactive molecules to generate the desired imaging probes. This method was applied to a wide range of aliphatic carboxylic acids, including complex and functionalized drug molecules, amino acids and short peptides. For non-stabilized radicals derived from benzylic and non-benzylic carboxylic acids, a copper co-catalyst was introduced to obtain the labeled nitriles, whereas metal-free conditions were applied to nitrogen-stabilized radical derived from a-amino acids and peptides to form the radiolabeled a-amino nitriles. These radiolabeled nitriles were then easily converted back to radiolabeled carboxylic acids.

The application discloses a method for preparing aromatic nitro compounds through photo-oxidation and reduction catalysis, and the method comprises the following steps: irradiating a compound of formula I with a nitrite and a photo-catalyst under LED light source to perform photo-oxidation and reduction catalysis reaction, so as to obtain the aromatic nitro compound. 5 The method has mild reaction conditions, can construct ¹ N-labeled aromatic nitro compounds in one step, and has good yield, thereby providing a convenient way for drug metabolism tracking and isotope labeling. The method has wide application prospects in the fields of organic synthesis, drug research and development and isotope labeling.

The present invention discloses a method for synthesizing 1,4-dicarbonyl quinoxalinone derivatives. Under photoredox catalysis, diazo compound B generates a radical precursor through a proton-coupled electron transfer (PCET) process to add to quinoxalin-2(1H)-one compound A. Subsequently, compound G is obtained through the isomerization of enamine and imine. The alkyl radical adds to the imine again, and finally, a 1,4-dicarbonyl quinoxalinone derivative is obtained through single electron transfer and deprotonation. This method uses visible light as a green energy source for driving, methanol and water as reaction solvents, and has mild reaction conditions and is easy to operate.

This invention discloses a method for synthesizing itaconic acid compounds. The method directly uses allyl ester compounds as raw materials, selects oxalic acid compounds or oxalate amine compounds as acylation reagents, uses triphenylphosphine as an additive, and employs metal-free 3,6,-di-tert-butyl-9-mesethyl-10-phenylacridine-10-tetrafluoroborate as a photo-redox catalyst. Under the catalysis of this organic photo-redox catalyst, corresponding acyl radicals and allyl radicals are generated, respectively. Through radical cross-coupling, itaconic acid compounds are finally obtained. This method has a wide range of applicable substrates, low preparation cost, and simple steps. It is convenient to operate, environmentally friendly, exhibits excellent stereoselectivity, and tolerates a broad spectrum of functional groups.

Described are methods for preparing a deuterated aldehyde using with a photocatalyst and a hydrogen atom transfer agent in a H2O free solvent comprising D2O and an organic solvent under an inert gas. The methods may be used to convert a wide variety of aldehydes (e.g., aryl, alkyl, or alkenyl aldehydes) to C-1 deuterated aldehydes under mild reaction conditions.

The invention provides an F-18 labeled PARP inhibitor as well as a preparation method and application thereof, and belongs to the technical field of biological medicines. The F-18 labeled PARP inhibitor provided by the invention can be used for realizing efficient radioactive labeling preparation by catalyzing a labeled precursor through photooxidation reduction. The tracer shows excellent PARP positive tumor imaging performance, can be used for accurate molecular imaging diagnosis of PARP positive tumors, and provides a visual monitoring means for evaluation of the treatment effect of a PARP inhibitor. The radiolabeled compound developed by the invention has good tumor targeted uptake ability and excellent tumor specific background ratio, can realize high-contrast imaging of PARP positive tumors, and provides a reliable basis for clinical diagnosis.

The application relates to a synthesis method of a 3-benzoylquinoxalin-2(1H)-one compound, which comprises the following steps: in a glove box, a photosensitizer fac-Ir(ppy)3 and a substrate quinoxalin-2(1H)-one are accurately weighed by using an analytical balance and added into a reaction tube, then a syringe is used to add a solvent into the reaction tube, a rubber plug is plugged, the reaction tube is shaken and taken out of the glove box; in the reaction tube containing the above-mentioned medicine, benzoic chloride and an organic base N,N-diisopropylethylamine are continuously added by using a micro-sampler; the reaction mixture is placed in a 20W blue LED light reaction generating device for reaction, the reaction is completed, the reaction liquid is concentrated by reduced pressure distillation to obtain a crude product, and the pure product is obtained by separation and purification; the application adopts a photo-oxidation and reduction catalysis strategy, uses cheap and easily obtained acyl chloride as an acyl source, can realize quinoxalin-2(1H)-one C-3 acylation reaction without the action of an oxidant, greatly reduces the cost of 3-benzoylquinoxalin-2(1H)-one synthesis, and has remarkable social and economic benefits.

The disclosure relates to photoredox catalysts (PC) and methods for the Birch reductions of aromatic substrates, such as benzene, benzeneoid, and heteroaromatic compounds, using light as the driving force. Certain aspects of the disclosure encompass methods for reduction of aromatic substrates. The method comprises contacting an aromatic substrate with a sacrificial electron donor in the presence of a photoredox catalyst in a solvent, thereby forming a reaction mixture; exposing the reaction mixture to visible or UV light under reaction condition sufficient to reduce the aromatic substrate compound.

The invention relates to a compound based on a diphenylamine derivative and a quinoxaline skeleton, a preparation method and an application as a photocatalyst, and belongs to the technical field of photocatalysis. The compound exhibits excellent photocatalytic efficiency and selectivity in an amination dehydrogenation aromatization reaction synergistically catalyzed by organic photoredox catalysis and cobalt oxime complexes, and can efficiently promote the synthesis of aromatic amine / heterocyclic amine compounds under mild visible light conditions. Compared with the prior art, the photocatalyst of the invention has higher catalytic activity and wider substrate applicability, has significant practical application value, can be effectively applied to the field of green organic synthesis, and is particularly suitable for the green synthesis process of aromatic amine compounds and drugs such as local anesthetic tetracaine.

The invention relates to a compound based on a diphenylamine derivative and a quinoxaline skeleton, a preparation method and application of the compound as a photocatalyst, and belongs to the technical field of photocatalysis, the compound shows excellent photocatalytic efficiency and selectivity in an amination dehydrogenation aromatization reaction of organic photooxidation reduction catalysis and cobalt oxime complex concerted catalysis, and the compound can be used for preparing a catalyst. Compared with the prior art, the photocatalyst disclosed by the invention has the advantages of higher catalytic activity, wider substrate applicability and remarkable practical application value, can be effectively applied to the field of green organic synthesis, and can be used for efficiently promoting synthesis of aromatic amine / heterocyclic amine compounds under a mild visible light condition. The method is especially suitable for green synthesis processes of aromatic amine compounds, local anesthetic cocaine and other drugs.

This invention relates to the field of fluorescent compound preparation technology, and discloses a method for synthesizing naphtho[1',2'4,5]imidazo[1,2-a]pyridine fluorescent compounds, including a cyclized compound, wherein the cyclized compound includes styrene compounds and imidazolium heterocyclic compounds, and the cyclized compound is a naphtho[1',2'4,5]imidazo[1,2-a]pyridine fluorescent compound; it also includes a method for synthesizing naphtho[1',2'4,5]imidazo[1,2-a]pyridine fluorescent compounds. This invention utilizes a synergistic combination of a photo-redox catalyst and a cobalt oxime catalyst to achieve a [4+2] cyclization reaction of olefins with imidazopyridines. Under photochemical conditions, imidazopyridine compounds and styrene compounds undergo a [4+2] cyclization reaction with the addition of the photo-redox catalyst and the cobalt oxime catalyst. This facilitates the rapid synthesis of naphtho[1',2'4,5]imidazo[1,2-a]pyridine fluorescent compounds. It avoids the use of precious metal catalysts or chemical oxidants, and the reaction conditions are mild, making it suitable for the mass production and processing of naphtho[1',2'4,5]imidazo[1,2-a]pyridine fluorescent compounds, reducing synthesis and production conditions, saving costs, and improving efficiency.

The invention generally relates to methods of making substituted arenes via direct C—H amination. More specifically, methods of making para- and ortho-substituted arenes via direct C—H amination are disclosed. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.

The method comprises the following steps: in a nitrogen atmosphere, mixing a compound 1, a compound 2, an oxidant, alkali, a photocatalyst and a solvent, carrying out a reaction under the conditions of room temperature and illumination, carrying out TLC monitoring until the reaction is completed, and carrying out separation and purification on the reaction mixture to obtain an isoquinoline diketone compound 3; the method disclosed by the invention is mild in condition, wide in substrate application range and capable of efficiently synthesizing the polysubstituted nitrogen-containing compound; .

The invention belongs to the technical field of preparation of alpha-aryl cyclic ketone compounds, and particularly relates to a method for preparing an alpha-aryl cyclic ketone compound through photooxidation reduction catalysis. The method comprises the following specific reaction processes: in an inert gas atmosphere, dissolving aryl halide and a cyclic ketone compound in a solvent, and carrying out a photooxidation reduction reaction under a light source with the wavelength of 390nm by taking imidazolium salt as an organic photooxidation reduction catalyst and taking pyrrolidine as a photocatalytic sacrificial agent, so as to obtain the target product alpha-aryl cyclic ketone compound. According to the invention, imidazolium salt is selected as an organic photooxidation reduction catalyst, so that not only can organic reaction of aryl halide containing strong electron withdrawing groups such as cyano and trifluoromethyl be promoted, but also organic reaction of aryl halide containing electron donating groups such as methyl and methoxyl can be promoted. In addition, the yield of the alpha-aryl cyclic ketone compound is effectively improved, and a new strategy is provided for the alpha-arylation reaction of the metal-free cyclic ketone compound.

The invention discloses a migration C (sp)-H / C (sp)-H cross-coupling reaction realized by metal / photooxidation reduction catalysis, and belongs to the field of organic chemistry and medicinal chemistry. Under the action of a metal nickel source, a photocatalyst, a ligand, alkali, an additive and the like, alkane and ortho-alkenyl substituted aryl halide or ortho-pyridine substituted aryl halide react in an organic solvent under illumination; a series of polysubstituted olefin or polysubstituted aromatic hydrocarbon compounds are obtained with excellent regioselectivity, stereoselectivity and good yield, and can be used as pharmaceutical active molecules. Cheap transition metal nickel is used as a catalyst, alkane and aryl halide which are simple and easy to obtain are used as raw materials, conditions are mild and simple, functional groups are good in compatibility, and operation is easy and convenient.