33 results about "Axial chirality" patented technology

This invention discloses an axially chiral 1,4'-biquinolinone and its derivatives, and a synthetic method thereof. The method uses MBH carbonate and quinoline-2(1 H Using β-ketones as raw materials, (DHQD)₂PYR as catalyst, and DME as solvent, a centrally chiral β-substituted allyl intermediate was synthesized; then, using iron powder as a reducing agent and acetic acid as solvent, enantiomeric enriched centrally chiral γ-lactam compounds were obtained; finally, using DBN as a base and DME as solvent, enantiomeric enriched compounds were obtained. (S) -Axial chiral 1,4'-biquinolinone or its derivatives. The method of this invention has mild reaction conditions, readily available raw materials, high enantioselectivity of the product, and excellent yield. The synthesized 1,4'-biquinolinone or its derivatives can be further used to synthesize novel substituted quinolinone phosphonate compounds, and to synthesize drugs with antibacterial, antimalarial, anticancer, antitumor, or herbicidal activities, showing broad application prospects.

The application relates to the technical field of organic chemical synthesis, and discloses an axially chiral porphyrin compound with a long-chain ester structure and a preparation method and application thereof. The compound has a structure shown in formula (I), formula (I), wherein R is n is 6, 8, 10, 12, 14 or 16. The method provided by the application has great significance for the study of an axially chiral long-chain compound family, and proves that the chain length of a raw material greatly influences the liquid crystal properties of an obtained axially chiral long-chain compound, and can inspire the synthesis of an axially chiral porphyrin compound with a longer chain.

The application discloses a method for constructing a cycloalkene-quinolinone axial chiral compound through a Heck reaction. The method uses a quinolinone compound containing central chirality as a substrate, uses palladium acetate (Pd(OAc)2) and 4,5-bisdiphenylphosphine-9,9-dimethylxanthene (Xantphos) as a catalyst, uses silver phosphate (Ag3PO4) as an alkali, and uses toluene as a solvent to prepare a cycloalkene-quinolinone axial chiral compound. The compound can be reacted with diisobutylaluminum hydride to realize conversion of a functional group. The method has mild reaction conditions, raw materials are easy to obtain, the product has excellent enantioselectivity, and has excellent yield, and thus provides a new method for synthesizing a cycloalkene-quinolinone axial chiral compound.

The application discloses an organic light-emitting material with chiral and narrow-band emission performance, a preparation method and application thereof, and the core is that multiple resonance structures can effectively inhibit the vibration coupling between S1-S0 transition and excited state structure relaxation, form significant narrow-band emission, and simultaneously utilize the axial chirality characteristics of BINOL, utilize a chiral disturbance strategy to form circularly polarized luminescence. The application further provides a preparation method of the material, wherein compound B is obtained by reacting compound C with compound D, and the organic light-emitting material is obtained by reacting compound A with compound B. The material has the characteristics of thermal activated delayed fluorescence induced by multiple resonance effect, and simultaneously has the characteristics of circularly polarized luminescence, and can be applied to the fields of 3D display, molecular probe, spin information, optical data storage and processing and optoelectronic devices, and the like. The synthesis process is simple, raw materials are widely sourced and inexpensive, and the material is suitable for wide application.

The invention belongs to the technical field of organic chemical synthesis, and particularly discloses a pyrazole-pyrrole atropisomer and a synthesis method thereof.The structure of the pyrazole-pyrrole atropisomer is as shown in the formula I. The method comprises the steps that 1, 4-diketone derivatives, aminopyrazole and a chiral protonic acid catalyst are sequentially added into a dry reaction container, stirring is performed for 1-3 h, and a reaction solution is obtained; and then adding an organic solvent as a reaction medium, and stirring at a certain temperature until the reaction is finished to obtain the axially chiral pyrazole-pyrrole atropisomer. The synthesis method disclosed by the invention has the advantages of high target compound yield, easiness in purification, excellent enantioselectivity, wide substrate application range, simplicity and convenience in post-treatment and the like.

This invention belongs to the field of chemical catalysis technology, and discloses a class of bridged carboxylic acid-containing bifunctionalized phosphine ligands or their racemates or enantiomers, as well as their preparation methods and applications. The bridged carboxylic acid-containing bifunctionalized phosphine ligands or their racemates or enantiomers of this invention have the structures shown in Formulas I-V: wherein, R 1 R' is a C1-C5 straight-chain alkyl group; R' is any one of substituted or unsubstituted aryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl. The bridged carboxylic acid-containing bifunctionalized phosphine ligand of this invention, with biphenyl as its backbone, achieves complete transfer of facet chirality to axial chirality through a desymmetry reaction via precise chiral recognition and control. The resulting chiral ligand exhibits advantages such as high reactivity, good enantioselectivity, and a wide substrate adaptability. It is particularly effective in palladium-catalyzed asymmetric C-H bond-activated arylization reactions of halogenated compounds and can be applied to asymmetric C-H bond-activated arylization reactions.

A kind of ethenyl indole and medium ring compound and its synthesis method, compound includes axial chiral ethenyl indole and nine-membered ring compound and ethenyl indole and eight-membered ring compound, structural formula is as shown in formula 3 and formula 6 respectively;Synthesis method: with formula 1 compound 3-ethynyl-2-indole methanol and formula 2 compound 2-indole ethanol / formula 5 compound 2-indole methanol as reaction raw material is added to organic solvent, additive is added, under the catalysis of catalyst and under certain temperature condition stirring reaction, TLC is tracked to complete reaction, filter, concentrate, purify and obtain.The ethenyl indole and medium ring compound synthesized in the application, through biological activity test, shows that the two types of derivatives have high sensitivity and strong cytotoxic activity to human prostate cancer cell PC-3.The reaction condition of the application is relatively conventional, the reaction process is mild, simple, low in cost, suitable for industrial large-scale production, and the application range of the method is widened.

This invention discloses a method for the kinetic resolution of oxaspirone via organocatalytic hydrogenolysis. Using chiral phosphate CPA as a catalyst, Hantzsch ester as a hydrogen source, and racemic oxaspirone 2,4-dien-6-one rac-1 as a substrate, a series of axially chiral biaryl phenolic compounds 2 are synthesized via asymmetric hydrogenolysis, and the central chiral oxaspirone 1 is recovered. This invention offers advantages such as simple and practical operation, readily available raw materials, high resolution coefficient, and good enantioselectivity. Some of the axially chiral biaryl products have structures similar to axially chiral cannabinol, possessing potential medicinal value.

This invention provides a method for preparing chiral N-tert-butylsulfonamide compounds. The method uses N-tert-butylsulfonylimide as a starting material, employs Mn(CO)₅Br and a chiral PNN ligand as catalysts, and an alcohol as a solvent. A hydrogenation reaction occurs in this homogeneous catalytic system, yielding axially chiral diaryl nitrophenol compounds in high yield (99%) and with high ee values ​​(>99%). This reaction has the advantages of high efficiency, mild conditions, and environmental friendliness. The obtained chiral N-tert-butylsulfonamide can be deprotected with a sulfonyl protecting group to obtain the corresponding chiral primary amine.

The invention relates to the technical field of organic chemical synthesis, in particular to a carbazole axially chiral tetra-substituted allene derivative which is a compound containing a structure shown in the formula (III), R1 is connected with a benzene ring, and R1, R2 and R3 are independently selected from H, alkyl, halogen, silicon, alkenyl, alkynyl, aryl, acyl, sulfonyl, heteroaryl and benzyl. Compared with the prior art, the carbazole axially chiral tetra-substituted allene derivative is obtained by combining the carbazole compound and the propargyl alcohol compound in an addition manner, and the carbazole axially chiral tetra-substituted allene derivative has an allene skeleton and a carbazole active fragment at the same time; the compound can be used as a potential skeleton for developing novel antibacterial and antitumor drugs.

The application discloses an axially chiral cyclopentenyl and indole-naphthyl compound and a preparation method and application thereof, and the structural formula of the compound is shown in formula 3 and formula 5. The formula 3 compound is obtained by stirring and reacting formula 1 and formula 2 compounds under the action of a chiral phosphoric acid catalyst. The formula 5 compound is obtained by synthesizing the formula 3 compound in two steps. Through biological activity testing, the formula 3 compound has significant cytotoxic activity on PC-3 cancer cells. Through model reaction verification, the formula 5 compound can be used as a chiral ligand or a chiral organic catalyst, and is respectively applied to catalyzing asymmetric allyl coupling reaction and catalyzing asymmetric (4+1) cycloaddition reaction. The method for preparing the axially chiral cyclopentenyl and indole-naphthyl compound is simple in operation, mild in reaction condition, economical and easy in raw material, high in optical purity of the prepared axially chiral compound, high in yield and good in application prospect.

The invention discloses a preparation method of 2-aza [5] helicene, and belongs to the field of organic synthesis. The preparation method comprises the following steps: firstly, taking commercialized 2, 3-dihydrophenanthrene-4 (1H)-ketone as an initial raw material, and generating a 4-bromo-1, 2-dihydrophenanthrene-3-formaldehyde compound through a Vilsmeier-Haack reaction; secondly, the 4-bromo-1, 2-dihydrophenanthrene-3-formaldehyde and the 2, 3-dichloro-5, 6-dicyanobenzoquinone are subjected to oxidative aromatization, and a 4-bromophenanthrene-3-formaldehyde compound is generated; then, a Suzuki coupling reaction is catalyzed through palladium, and axial chirality 4-(4-methylpyridine-3-yl) phenanthrene-3-formaldehyde is constructed; and finally, carrying out intramolecular Aldol condensation / cyclization reaction to realize'shaft-to-screw 'transfer, so as to successfully obtain the target product 2-aza [5] helicene. The raw materials adopted by the method are cheap and easy to obtain, and the synthesis method is simple to operate and meets the requirements of industrial production.

The invention relates to the technical field of biological engineering and biological catalysis, in particular to an alcohol dehydrogenase mutant and application thereof. The invention discloses an alcohol dehydrogenase mutant CpAR2-M5 (F85A / T125S / F192L / E209A / I213F). The corresponding amino acid sequence of the alcohol dehydrogenase mutant CpAR2-M5 is shown as SEQ ID No. 3. The invention also discloses a preparation method of the alcohol dehydrogenase mutant CpAR2-M5. The S-configuration axial chiral biaryl dimethyl carbinol compound can be applied to dynamic kinetic resolution asymmetric reduction of the biaryl dimethyl carbinol compound so as to prepare the S-configuration axial chiral biaryl dimethyl carbinol compound, the highest yield can reach 95%, the highest stereoselectivity can reach 99% ee, and a green, efficient and high-stereoselectivity synthesis strategy is provided for subsequent synthesis of the compound.

The application provides a kind of axially chiral biaryl bisphosphine ligand, with structure shown in formula I.The chiral ligand can be combined with transition metal to form chiral catalyst, and shows excellent catalytic performance; the above-mentioned ligand provided by the application has simple synthesis route, and two kinds of chiral ligands can be obtained respectively, and corresponding racemate, levorotatory body and dextrorotatory body can also be obtained; raw materials are easy to obtain, and corresponding ligand library can be conveniently established for high-throughput screening of many phosphine or nitrogen involved asymmetric catalytic reactions, so as to obtain excellent new ligands suitable for certain asymmetric catalytic reactions; the nitrogen atom contained in the bisphosphine ligand skeleton can be coordinated with metal catalyst, and can also act as internal base for certain reactions, and is expected to be applied to certain catalytic reactions requiring addition of alkali to promote.

The application relates to the technical field of chemical synthesis, and particularly discloses an indole pyrazole C-N axis chiral compound and a synthesis method thereof. The structural formula of the indole pyrazole C-N axis chiral compound is shown in formula (I), the compound is a kind of axis chiral compound with high resistance to selection, R1 is a substituted or unsubstituted phenyl, naphthyl or alkyl, R2 is a phenyl, R3 is a substituted or unsubstituted phenyl, and R4 is an ethyl. The compound shown in formula (I) can inhibit the growth of cancer cells, thereby interfering with the malignant behavior of the cancer cells.

The invention relates to the technical field of chemical synthesis, and particularly provides a C-6 axially chiral 2-pyrone compound as well as a preparation method and application thereof. The structural formula of the C-6 axial chiral 2-pyrone compound provided by the invention is as shown in the following formula 3. The C-6 axially chiral biaryl 2-pyrone compound provided by the invention can be directly used as a high-efficiency catalyst to be applied to an asymmetric catalytic reaction, shows excellent catalytic performance and has relatively high application value, and the preparation method is simple and convenient to operate, low in energy consumption and green and environment-friendly. 3.

The invention discloses a multi-chiral alpha-amino phosphate compound as well as a preparation method and application thereof, and belongs to the technical field of organic synthesis. According to the invention, the asymmetric cyclization-phosphination reaction of the o-alkynyl imine and the phosphite ester is catalyzed by using the metal-based catalyst, and the cyclization process of the o-alkynyl imine can be efficiently induced through a metal / chiral oxazoline ligand catalytic system, so that the aza-alkenyl metal intermediate with C-N axial chirality is formed; the alpha-amino phosphate compound with both C-N axial chirality and carbon center chirality is finally obtained by further constructing carbon center chirality through nucleophilic addition of phosphite, the yield is high, the enantioselectivity is good, the reaction conditions are mild, the raw materials are simple and easy to obtain, the substrate applicability is wide, multiple chiral centers can be efficiently constructed, and the method is suitable for industrial production. The atom economy is high; and the method has practicability and amplification potential, and the product yield and enantioselectivity are not obviously reduced.

This invention discloses an N-N axial chiral phase-transfer catalyst, its synthesis method, and its applications, belonging to the field of asymmetric catalytic synthesis technology. Using chiral 2,4-pentanediol and N-Boc-indolephenol as starting materials, this invention efficiently constructs an N-N axial chiral biscarbazole cyclic ether skeleton through a five-step reaction involving Mitsunobu etherification, deBoc protection, PIDA oxidative cyclization, radical bromoxymethylation, and intramolecular quaternization. This method eliminates the need for complex chiral resolution and noble metal coupling, employs mild reaction conditions, uses readily available and inexpensive starting materials, achieves high overall yield, and yields a product with an axial chirality ee value ≥98%. The resulting catalyst possesses excellent conformational rigidity, chiral induction ability, and phase-transfer performance, exhibiting broad substrate applicability. It also possesses bisindole ring bioactivity, making it widely applicable in asymmetric catalytic synthesis in pharmaceuticals, fine chemicals, and other fields, and providing new directions for the development of antibacterial and antitumor biomaterials.

The application belongs to the field of bioengineering and biocatalysis technology, and particularly relates to an alcohol dehydrogenase mutant and application thereof. The application discloses an alcohol dehydrogenase mutant CcPAR-M1 (V158L), and an amino acid sequence of the mutant is shown as SEQ ID No. 3. The mutant can be used for catalyzing asymmetric reduction reaction of a biaryl aldehyde substrate through dynamic kinetic resolution to generate R an axially chiral biaryl dimethanol compound. By using the biocatalytic system disclosed in the application, the highest yield of the target product can reach 96%, and the enantiomeric excess value can reach 99% ee at most. The method provides a green, efficient and excellent stereoselective biocatalytic strategy for construction of the axially chiral biaryl dimethanol compound.

The invention discloses a cyclic olefin axial chiral compound and a synthesis method thereof. According to the method, cyclic beta-ketene and 2-sulfonyl indole are used as raw materials, an allyl palladium chloride dimer and 4-tert-butyl-2-[2-(diphenylphosphino) phenyl]-4.5-dihydrooxazoline are used as catalysts, 1, 8-diazabicyclo [5.4. 0] undec-7-ene is used as alkali, and the cyclic olefin axial chiral compound is synthesized through a one-pot method. The method is mild in reaction condition, high in product selectivity and excellent in yield, and the synthesized cyclic olefin axial chiral compound is suitable for developing indanone drugs.

The invention discloses a method for synthesizing an axially chiral gamma-carbazolone derivative, and belongs to the field of organic chemistry. An indole-3-amide compound 1 and an alkyne compound 2 are used as raw materials, and in the presence of a catalyst Mn (OAc) 3.2 H2O, the axially chiral gamma-carbazolone derivative is obtained through cobalt-catalyzed C-H activation / cyclization. The method is mild in reaction condition and environment-friendly, the axially chiral gamma-carbazolone derivative can be obtained with high yield and high enantioselectivity, and a simple and effective synthesis way is provided for the axially chiral gamma-carbazolone derivative.

The present invention relates to the field of asymmetric catalysis and organic synthesis, and specifically provides a general method for generating axial chirality by means of a chiral companion strategy. The features and concept of the method are: a chiral aromatic tertiary amine compound without a nitrogen chiral center is subjected to intramolecular chiral oxidation to induce the formation of a new aromatic tertiary amine N-oxide (NO) chiral center. Due to the structural rigidity of the chiral aromatic tertiary amine N-oxide compound, when the steric hindrance of different substituents Rb and Rs connected to ortho positions of an aromatic ring is relatively large, the rotation of the aromatic ring is hindered, and new rotation-hindered axial chirality is generated while an aromatic tertiary amine chiral N-oxide center is formed. By means of the method and by regulating the structural and functional characteristics of the different substituents Rb and Rs, various axial chiral ligands, chiral small-molecule catalysts, pharmaceutical and agrochemical intermediates, and chiral synthons can be prepared. The present invention has important scientific and application values for the design, synthesis, and application of chiral ligands, chiral catalysts, especially ligands and catalysts containing axial chirality, and chiral compounds having special functions.

The invention discloses a fluoreno [c] isoquinolinone derivative with an axial chiral element, and the fluoreno [c] isoquinolinone derivative has at least one of the following structural formulae shown in the formula I and the formula II: a preparation method comprises the following steps: taking a substituted indene diene compound and high phthalic anhydride as raw materials, and under the action of a chiral catalyst or an alkali catalyst, carrying out aromatization promoted cascade bicyclic reaction to obtain the fluoreno [c] isoquinolinone derivative with the axial chiral element. A fluoreno [c] isoquinolinone skeleton with axial chiral elements is efficiently constructed under mild conditions. The method has the advantages of wide substrate application range, good enantioselectivity, high reaction efficiency and the like. The derivative disclosed by the invention shows strong blue fluorescence in a solid state, can be applied as an organic photoelectric material or a fluorescent material, and particularly has a wide prospect in the field of solid luminescent materials.

The invention belongs to the technical field of organic chemical synthesis, and particularly relates to an N-N axial chiral monophosphine ligand as well as a preparation method and application thereof. The structure of the N-N axial chiral monophosphine ligand is shown as a formula I and a formula II, wherein in the formula I and the formula II, Ar is aryl, substituted aryl or heteroaryl; r < 1 >-R < 3 > are respectively and independently selected from hydrogen, aryl, substituted aryl, heteroaryl, alkyl, alkylene and halogen. The N-N axial chiral monophosphine ligand is constructed by taking a phosphine-containing indole derivative and acrylate as raw materials under the action of an iridium catalyst and a chiral ligand. The ligand can be used for carbonyl reduction reaction catalyzed by rhodium and coupling reaction catalyzed by palladium, and shows excellent enantioselectivity; the conjugated structure of indole and pyrrole is combined with the electronic characteristics of phosphine groups, so that the compound is expected to be applied to the development of organic photoelectric materials and bioactive molecules. The method provides a wide space for developing a novel efficient chiral catalyst, and has a very good application prospect.

The invention discloses an open-chain imine axially chiral compound and a synthesis method thereof. According to the method, MBH carbonate and a (2-methoxynaphthalene-1-yl) (phenyl) methylenimine derivative are taken as raw materials, palladium acetate and a chiral phosphoramidite ligand are taken as catalysts, lithium carbonate is taken as alkali, methylbenzene is taken as a solvent, and the enantiomer-enriched open-chain imine axially chiral compound is obtained. The compound can react with m-chloroperoxybenzoic acid to realize efficient conversion from axial chirality to central chirality. The method has the advantages of mild reaction conditions, easily available raw materials, high product enantioselectivity and excellent yield, and provides a simple and efficient way for preparation and conversion application of open-chain imine axially chiral compounds.

The invention discloses an axially chiral N-heterocyclic carbene ligand as well as a preparation method and application thereof. The axially chiral N-heterocyclic carbene ligand has a structure as shown in a general formula (I), wherein an axially chiral part A of the ligand is any one of A-1 or A-2; the part B of the ligand is any one of B-1 and B-2 or is the same as A; and the anion X part of the ligand is any one of chlorine, bromine, iodine, tetrafluoroborate or hexafluorophosphate. The axially chiral N-heterocyclic carbene ligand and a transition metal compound are subjected to in-situ complexation in a reaction system to form a complex catalyst, and the complex catalyst shows good yield and enantioselectivity in amylene amide substrate intramolecular amination and arylation reaction and has a good industrial application prospect. The invention belongs to the field of asymmetric synthetic chemistry.

The application discloses a kind of chiral N -(4-indolyl)imidazole and its N’ Functional imidazole salt derivatives; the application is obtained by chiral resolution N -(1,3,5,7-tetramethyl-2-ethyl-4-indolyl)-4,5-dimethyl imidazole R a type and S a type isomers, then react with halogenated hydrocarbon, first obtain axially chiral N Chiral nitrogen heterocyclic carbene precursor imidazole salt of arylimidazole skeleton; the chiral N -(4-indolyl)imidazole salt can be applied in asymmetric catalytic reaction as catalyst or ligand.

The application discloses a kind of structural flexible electron-donating characteristics of axial chirality pyridine amide, quinoline amide nitrogen ligand.This chiral nitrogen ligand core structure features include binaphthalene axial chirality skeleton and have flexible electron-donating ability pyridine amide, quinoline amide unit.The chiral binaphthalene pyridine amide, quinoline amide nitrogen ligand provided by the application can be directly applied to palladium-catalyzed asymmetric suzuki coupling reaction and copper-catalyzed olefin difunctionalization radical reaction, exhibits higher catalytic activity.Application in radical reaction yield can reach 72%;In asymmetric suzuki coupling reaction, yield can also reach 72%, enantioselectivity can reach 18%.The ligand uses binaphthyl methyl ester as starting material, synthesis route is reliable, synthesis efficiency is high, with good practical prospect.The application provides an important reference for efficient synthesis of new chiral pyridine amide, quinoline amide nitrogen ligand and catalytic application of the ligand.