97 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 invention discloses an axially chiral aryl pyrrole derivative, a preparation method thereof and application of the axially chiral aryl pyrrole derivative as a chiral catalyst, and relates to the technical field of organic matter synthesis. According to the invention, substituted primary amine and enyne are taken as raw materials and react in the presence or absence of an additive in the presence of a copper salt and a PyBOX ligand to obtain a novel axially chiral aryl pyrrole derivative, and a method for forming an aryl pyrrole rotation-hindered isomer through [1 + 4] cyclization of the primary amine and electron-deficient enyne under the catalysis of metal is developed. According to the present invention, the used catalyst is easily available, the preparation cost is low, the synthesis method is suitable for a variety of substrates, a variety of axially chiral aryl pyrrole compounds with novel structures can be constructed, and the obtained aryl pyrrole compound has characteristics of high yield and excellent enantioselectivity. The synthesis route of the aryl pyrrole compound is expanded, and a foundation is laid for further exploration and application of the compounds in asymmetric catalysis, drug development and other chemical fields.

The invention discloses a chiral P, N, N-tridentate ligand based on a ferrocene skeleton as shown in a formula I, a preparation method of an iridium catalyst containing the ligand and application of the ligand in preparation of a carbon-nitrogen axial chiral compound and a diltiazem intermediate. According to the present invention, the chiral P, N, N-tridentate ligand based on the ferrocene skeleton and the metal iridium precursor [Ir (COD) Cl] 2 are subjected to complexation to obtain the complex as the iridium catalyst, and the catalyst can be used as the iridium catalyst with characteristics of high yield (up to 99%), high enantioselectivity (up to gt; 99% ee) and high diastereoselectivity (up to gt; according to the method, N-aryl indolal or N-aryl indolone is subjected to asymmetric hydrogenation by using N-aryl indolal or N-aryl indolone (R1, R2, R3, R4, R5, R6, R7, R7, R8, R9, R9, R9, the catalyst can also be applied to asymmetric synthesis of diltiazem intermediate (2R, 3S)-3-(4-methoxyphenyl)-2, 3-epoxidized propionate, has the advantages of short synthesis route, high yield, good stereoselectivity (as high as 99% ee, 97 / 3dr) and the like, and has better economic and social benefits.

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 invention discloses a chiral 6-NH2 uracil compound as well as a preparation method and application thereof, and belongs to the technical field of chemical synthesis. The invention provides a method for constructing C-N axial chiral 6-NH2 uracil and a corresponding amide compound thereof through asymmetric organic catalysis, under the catalysis of chiral phosphoric acid, racemization 6-NH2 uracil and azlactone are used as reaction substrates, and 6-amide uracil with optical activity is obtained by utilizing a kinetic resolution strategy. And the 6-NH2 uracil compound with optical activity is recovered. According to the method, chiral uracil is constructed by using an asymmetric catalysis strategy for the first time, and the method has the characteristics of convenience in operation, cheap and easily available raw materials, and high yield and enantioselectivity. The C-N axial chiral uracil shows excellent anti-tumor cell activity, and especially has excellent biological activity on colon cancer, cervical cancer, multiple myeloma, prostate cancer cells and the like.

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 relates to optically active diphenol with both central chirality and axial chirality as well as a synthesis method and application of the optically active diphenol. The structural formula of the optically active diphenol is as follows: # imgabs0 #, wherein Ar1 is an aryl compound or a heteroaryl compound with different substituent groups, Ar3 is an aryl compound with different substituent groups, Ar2 is an aryl compound or a heteroaryl compound with different substituent groups, and Ar4 is halogen or hydrogen. The invention focuses on an enantioselective synthesis method for constructing a diphenol compound NAPOLs with rigid conformation. The synthesis method comprises the following steps: catalyzing 1-aryl ethynyl-2-naphthol and a derivative thereof and 8-aryl hydroxymethyl-2-naphthol and a derivative thereof through chiral phosphoric acid to synthesize an optically active NAPOLs diphenol ligand with axial chirality and central chirality. The compound has the characteristics of central chirality and axial chirality, and is expected to provide a new idea for the field of asymmetric synthesis.

The invention discloses a method for stereodivergently synthesizing tetra-substituted axially chiral quinolinone. According to the method, MBH carbonate and quinolin-2 (1H)-ketone are used as raw materials, cinchona alkaloid is used as a catalyst, DME is used as a solvent, a quinolinone central chiral compound is synthesized, DBU or sodium methoxide is used as alkali, toluene is used as a solvent, and enantiomer-enriched E-or Z-tetra-substituted axially chiral quinolinone is obtained. The method has the advantages of mild reaction conditions, easily available raw materials, high product enantioselectivity and excellent yield, and provides four stereoisomers (S, E), (R, E), (S, Z) and (R, Z) under specific conditions.

The present invention discloses a rapid synthesis method for axially chiral aromatic amine compounds using metal-free catalysis. 1-substituted tetrahydro-2-naphthalenone and a cheap and readily available chiral amine are used as raw materials. Axial chiral aromatic amines are prepared by reaction under the action of a catalyst, and a wide range of substrates can be selected. Compared with traditional synthesis methods, the method of the present invention uses metal-free catalysis, has the advantages of simple conditions, convenient operation, relatively high yield, low environmental pollution, and ease of industrial production. The synthesis method of the present invention can simultaneously obtain two axially chiral aromatic amine compounds, and the yield range is 20%-70%.

The present invention discloses a method for synthesizing a 1-azafluorene compound and a 1-azafluorene compound containing a chiral axis at position 4. The specific method used in the present invention is to add a nickel catalyst, a ligand, an acetylenic nitrile compound and a Lewis acid additive to a solvent and stir, then add another acetylenic compound to the mixture, and after the reaction is completed, separate and purify to obtain a 1-azafluorene compound or a 1-azafluorene compound containing a chiral axis at position 4. The method realizes a one-step synthesis from an acetylenic nitrile compound and an alkyne to a 1-azafluorene skeleton, has the advantages of simple and safe operation, easy availability of raw materials, mild reaction conditions, high reaction efficiency and high enantioselectivity, and the prepared series of 1-azafluorene compounds can be widely used in the fields of organic chemical synthesis and medicinal chemistry.

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.

The invention discloses an axially chiral picolinamide and quinoline amide nitrogen ligand with a flexible electron donating characteristic in structure. The core structure of the chiral nitrogen ligand is characterized by comprising a binaphthalene axial chiral skeleton and picolinamide and quinoline amide units with flexible electron donating capability. The chiral binaphthyl picolinamide and quinoline amide nitrogen ligand provided by the invention can be directly applied to an asymmetric Suzuki coupling reaction catalyzed by palladium and an olefin bifunctional free radical reaction catalyzed by copper, and shows relatively high catalytic activity. The yield can reach 72% when the catalyst is applied to a free radical reaction; in an asymmetric Suzuki coupling reaction, the yield can also reach 72%, and the enantioselectivity can reach 18%. The ligand takes binaphthyl methyl ester as an initial raw material, is reliable in synthesis route and high in synthesis efficiency, and has a good practical prospect. The invention provides important reference for efficient synthesis of novel chiral picolinamide and quinoline amide nitrogen ligands and catalytic application of the ligand.

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 discloses an axially chiral phenanthroline ligand as well as a preparation method and application thereof. The axially chiral phenanthroline ligand has a structure as shown in a general formula (I), wherein an axially chiral part of the ligand is a binaphthyl structure A; r1 in the binaphthalene structure A of the ligand is any one of alkyl, phenyl and substituted phenyl; and the part B of the ligand is selected from any one of hydrogen, halogen, phenyl and substituted phenyl or is the same as A. According to the invention, an axially chiral phenanthroline ligand and a copper salt form a complex catalyst in situ in a reaction system, and a diverse substituted 1, 1 '-biphenyl-2'-iodine-2-amide compound with high optical purity and a 1, 1 '-biphenyl-2'-iodine-2-amide compound with high optical purity are respectively synthesized by catalyzing asymmetric ring-opening amination and ring-opening acylation of a ring-shaped diaryl iodonium salt. According to the present invention, in the reaction of the 1, 1 '-biphenyl-2'-iodine-2-carboxylic ester compound, the good to excellent yield, the enantioselectivity and the good substrate universality are represented, and the good industrial application prospect is provided. The invention belongs to the field of asymmetric synthetic chemistry.

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 invention belongs to the technical field of axially chiral phosphine catalysts, and particularly relates to a phosphine catalyst / ligand of a chiral indoloquinoline skeleton and a preparation method of the phosphine catalyst / ligand, and the phosphine catalyst / ligand is prepared by taking a compound 1 axially chiral compound 1-(6-phenylindolo [1, 2-a] quinazoline-7-yl) naphthalene-2-alcohol as a key precursor and adding a compound 2-(2-phenylindolo [1, 2-a] quinazoline-7-yl) naphthalene-2-alcohol as a ligand. A hydroxyl group of the compound 1 and a carboxylic acid group in a 2-(aryl phosphino or alkyl phosphino) benzoic acid compound 2 are subjected to a condensation reaction under the condition that a molecular sieve serves as a condensing agent, and the catalyst is prepared. The defects of a traditional axially chiral phosphine catalyst in the aspects of chiral regulation and control capability and substrate applicability can be effectively overcome, and a brand new design strategy is provided for developing an efficient and high-selectivity asymmetric catalytic system.

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 an axially chiral nitrogen-containing heteroaromatic ring amide ligand as well as a preparation method and application thereof. The axial chiral nitrogen-containing heteroaromatic ring amide ligand has a structure shown in a general formula (I), the structure shown in the general formula (I) is formed by connecting an axial chiral binaphthyl structure part A and a quinoline or phenanthroline part B through an amido bond, a nitrogen-containing heteroaromatic ring amide part can be chelated and coordinated with transition metal ions, and the binaphthyl structure provides a chiral environment for the ligand. A complex formed in situ by the axially chiral nitrogen-containing heteroaromatic amide ligand and palladium salt in a reaction system shows good catalytic activity and enantioselectivity in an intramolecular amination alkylation reaction for catalyzing olefin, and has a very good application prospect. The invention belongs to the field of asymmetric synthetic chemistry.

The application discloses a preparation method of N-N axial chiral isoquinoline ketone derivatives. A compound shown in formula 1 is used as a substrate, a decarboxylation intermolecular acetylene reaction is carried out with an alkyne shown in formula 2 in the presence of a cobalt catalyst and a Salox ligand L, and an N-N axial chiral isoquinoline ketone derivative with a structure shown in formula 3 is generated, and a reaction formula is as follows: in formula 1 and formula 3, Ar is a phenyl group, a substituted phenyl group or a naphthyl group, and the substituent of the substituted phenyl group is selected from halogen, acetylamino, methyl or tert-butyl; in formula 2 and formula 3, R 2 is selected from methyl, ethyl, propyl or butyl; and a directing group containing R 1 in formula 1 and formula 3 is selected from the following structures. The preparation method has the advantages of low catalyst consumption, mild reaction conditions, simple operation, wide practicability of substrates, good stereoselectivity and high yield, and has great application value.

The invention discloses a dicarbazole axially chiral fused ring compound and an organic electroluminescent device thereof, the organic compound has a structure as shown in a general formula I. A 3, 3 '-dicarbazole structural unit is used as a chiral center, a steric hindrance group is introduced to an ortho-position, and the dicarbazole axially chiral fused ring compound has a rigid and stable axially chiral structure, so that chiral induction is enhanced; one or two multi-resonance units are connected to a carbazole amino group, and a highest occupied molecular orbital (HOMO) and a lowest unoccupied molecular orbital (LUMO) are induced to be positioned on different atoms through a multi-resonance effect, so that the bonding / anti-bonding characteristic between the atoms is weakened; the change of electron density between atoms generated by radiative transition from the lowest excited state to the ground state is greatly reduced, so that telescopic vibration is reduced, and narrow spectrum emission is effectively realized; according to the present invention, with the application of the chiral-induced spin selectivity effect in the OLED light-emitting layer, the high EQE and the high circular polarization electroluminescent factor of the corresponding circular polarization electroluminescent OLED can be achieved on the basis of the chiral-induced spin selectivity effect. # imgabs0 #

The invention discloses a TBSADH alcohol dehydrogenase mutant as well as a preparation method and application thereof in the technical field of biology. The amino acid sequence of the TBSADH alcohol dehydrogenase mutant is shown as SEQ ID No. 1. The TBSADH alcohol dehydrogenase mutant is obtained by taking a TBSADH enzyme as a template through gene modification. The TBSADH alcohol dehydrogenase mutant can be applied to the biological synthesis of axially chiral alkylene ketone and alcohol compounds. The TBSADH alcohol dehydrogenase mutant has relatively high catalytic activity, is environment-friendly and is simple and convenient to operate.

The invention discloses a preparation method of an axially chiral allylamine compound, and relates to the technical field of organic synthesis. According to the method, in an organic solvent, aliphatic amine and (E)-2-(2-alkoxynaphthalene-1-yl)-3-aryl allyl benzoate react in the presence of a palladium catalyst, a chiral phosphorus ligand and BSA (Bovine Serum Albumin) to obtain a target product, namely the axially chiral allyl amine compound. The structures of the compounds are represented by 1H NMR, 13C NMR and HRMS and are confirmed. The invention provides a brand-new synthesis method of the axially chiral allylamine compound, the synthesis of the axially chiral allylamine compound is successfully realized by carrying out nucleophilic attack on the allylic palladium intermediate through the nitrogen nucleophilic reagent and directly carrying out asymmetric allylic substitution reaction, the reaction conditions are mild, the substrate applicability is wide, the yield is high, and the method is suitable for industrial production. The method has good application value and prospect.

The invention discloses a chiral benzoxazine diphosphine ligand and a complex and application thereof. The structure of the chiral benzoxadiphosphine ligand is shown as a formula (I), and in the formula (I), R1 is alkyl or aryl, R2 is alkyl or aryl, and R3 is at least one of fluorine, carbazolyl and 2, 6-dimethoxyphenyl. The chiral benzoxazine diphosphine ligand disclosed by the invention can be applied to two asymmetric reactions, namely cross dehydrogenation coupling of disilane hydrogen and benzyl alcohol under catalysis of rhodium and axial chiral Heck reaction of aryl trifluoromethanesulfonate and alkenyl ether under catalysis of palladium, and has excellent activity and relatively high enantioselectivity in the two asymmetric reactions; moreover, the chiral benzoxadiphosphine ligand can be directly synthesized from simple and easily available chiral aldehyde, and the preparation method is simple and easy to operate.

In one aspect, the disclosure relates to axially chiral cannabinoid analogs and methods of making the same. In one aspect, several tetracyclic scaffolds can be prepared from O-propargyl vinyl coumarins in good yields. In a further aspect, these tetracyclic scaffolds can be treated with a reductant to form the axially chiral cannabinoid analogs. In another aspect, the axially chiral cannabinoid analogs are shelf stable and maintain a three-dimensional structure during storage, enabling superior recognition of biological targets such as cannabinoid receptors. Also disclosed herein are prochiral cannabinoid analogs that can be synthesized from axially chiral cannabinoid analogs.

The invention discloses a preparation method of an axially chiral biaryl aminophenol compound, which mainly comprises the following steps: adding biaryl amino diphenol, di-tert-butyl dicarbonate ester and a chiral isothiourea catalyst into an organic solvent, cooling to-10 to-30 DEG C for reaction, and after the reaction is completed, separating and purifying to obtain the axially chiral biaryl aminophenol compound. And performing post-treatment to obtain the axially chiral biaryl aminophenol compound. The preparation method can be carried out under mild conditions, is good in stereoselectivity, convenient to operate and simple in post-treatment, and avoids the use of a heavy metal catalyst which may remain in a product; according to the present invention, the reaction raw materials are cheap and easily available, the compatibility of the substrate functional group is good, the amplification treatment can be conveniently performed, the practicability is strong, the diversified axially chiral biaryl aminophenol compound can be designed and synthesized according to the actual requirement, the operation is convenient, and the applicability of the method is widened.