JP5433850B2 - Optically active helical polymer with coordinating side chains - Google Patents

Description

  The present invention relates to an optically active helical polymer having a coordinating side chain and a chiral polymer catalyst in which a coordinating side chain and a metal are coordinated.

  Synthetic polymers around us generally have a random structure, whereas biopolymers represented by DNA and proteins have many spirals in one direction. Therefore, in recent years, artificial synthesis of not only biopolymers but also spiral polymers in one left-right direction has been studied.

  For example, Y. Ito et al., J. Am. Chem. Soc., 1998, 120, 11880 and M. Suginome et al., Org. Lett., 2002, 4, 351 include complete asymmetric living polymerization. Optically active helical polymers with helical direction control are disclosed. However, these documents do not disclose introduction of a substituent having functionality in the side chain, nor do they disclose that the helical polymer is given further functionality and is specifically utilized.

  By the way, with the increase in demand for optically active compounds in the pharmaceutical industry and material science, asymmetric organic synthesis has achieved rapid development. In particular, the catalytic asymmetric synthesis method using an optically active molecular catalyst is able to obtain a large amount of optically active products from a small amount of optically active sources (asymmetric molecular number amplification). Yes. For further development in this field, there is a strong demand for the development of chiral catalysts that are completely different from conventional designs. Chiral polymer ligands are starting to attract attention as next-generation practical chiral ligands in that they can provide chiral reaction fields that cannot be constructed with low-molecular-weight ligands and are easy to recover and reuse. .

  However, most chiral macromolecules with ligands simply have an excellent chiral low molecular weight ligand supported on the polymer, and chiral catalysts based on low molecular weight compounds with optical activity are However, there is a problem that a great amount of labor is often spent in synthesizing an optically active substance, and the selectivity does not exceed the selectivity when a low molecular ligand as a base is used.

  M. Reggelin et al., Proceeding of the National Academy of Sciences of the USA, 2004, 101, 5461 used polymethyl methacrylate having a side chain in which palladium is coordinated to the ligand. Asymmetric synthesis is disclosed. The polymer ligand has a bulky structure, and the main chain has a helical structure, and thus has optical activity. However, since polymethyl methacrylate, the main chain, is flexible, the helical structure is unstable, and asymmetric synthesis using the polymer must be carried out avoiding high temperatures. There is a problem that racemization easily occurs in each process of recovery and purification.

  An object of the present invention is to provide a novel optically active helical polymer having a site capable of coordination with a metal. Furthermore, the present invention provides an optically active helical polymer having a coordinating side chain and a chiral polymer catalyst as a highly selective asymmetric catalyst system utilizing the chiral polymer structure itself for the construction of an asymmetric reaction field. For the purpose.

  The present invention relates to an optically active helical polymer containing a unit represented by the following formula (1).

(In the formula, R ^{1 to} R ⁴ are each independently a hydrogen atom, an optionally substituted linear or branched alkyl group, an aliphatic hydrocarbon group having an unsaturated double bond, or cyclic alkyl. Group, aryl group, aromatic heterocyclic group, aliphatic heterocyclic group, halogen atom, cyano group, nitro group, carboxyl group, amino group, alkoxyl group, carbamoyl group, alkoxycarbonyl group and perfluoroalkyl group R ^{1 to} R ⁴ are the same or different and R ¹ and R ³ , R ³ and R ⁴ or R ⁴ are groups having at least one site capable of coordinating with a metal. And R ² may each form a ring.)

  The optically active helical polymer of the present invention preferably further contains a unit represented by the following formula (2).

(In the formula, each of R ^{5 to} R ⁸ independently represents a hydrogen atom, an optionally substituted linear or branched alkyl group, an aliphatic hydrocarbon group having an unsaturated double bond, or cyclic alkyl. Group, aryl group, aromatic heterocyclic group, aliphatic heterocyclic group, halogen atom, cyano group, nitro group, carboxyl group, amino group, alkoxyl group, carbamoyl group, alkoxycarbonyl group and perfluoroalkyl group R ^{5 to} R ⁸ may be the same or different, and R ⁵ and R ⁷ , R ⁷ and R ^8, or R ⁸ and R ⁶ may each form a ring. .)

  The optically active helical polymer of the present invention is preferably a copolymer.

  In the optically active helical polymer of the present invention, the group having a site capable of coordinating with a metal is preferably a group having a phosphorus atom, a nitrogen atom or a sulfur atom. The site capable of coordinate bond is preferably one that is coordinate-bonded to a metal. The metal is preferably at least one selected from the group consisting of elements of groups 4 to 16 and lanthanide elements in the 4th to 6th periods.

  The present invention also relates to a chiral polymer catalyst using the optically active helical polymer.

  The present invention relates to an optically active helical polymer containing a unit represented by the following formula (1).

In the formula, each of R ^{1 to} R ⁴ independently represents a hydrogen atom, an optionally substituted linear or branched alkyl group, an aliphatic hydrocarbon group having an unsaturated double bond, or a cyclic alkyl group. Selected from the group consisting of aryl group, aromatic heterocyclic group, aliphatic heterocyclic group, halogen atom, cyano group, nitro group, carboxyl group, amino group, alkoxyl group, carbamoyl group, alkoxycarbonyl group and perfluoroalkyl group And at least one of them is a group having a site capable of coordinating with a metal. R ^{1 to} R ⁴ may be the same or different, and R ¹ and R ³ , R ³ and R ^4, or R ⁴ and R ² may each form a ring.

  The linear or branched alkyl group preferably has 1 to 18 carbon atoms. Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, and a tert-butyl group.

  The number of carbon atoms of the aliphatic hydrocarbon group having an unsaturated double bond is preferably 1-18. Specific examples of the aliphatic hydrocarbon group having an unsaturated double bond include an alkylene group having 2 to 18 carbon atoms such as a vinyl group and an allyl group, an ethynyl group, and a propargyl group.

  It is preferable that carbon number of a cyclic alkyl group is 3-10. Specific examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.

  The aryl group preferably has 6 to 14 carbon atoms. Specific examples of the aryl group include phenyl group, xylyl group, benzyl group, tolyl group, naphthyl group, anthryl group, phenanthryl group, and azulenyl group.

  Examples of the aromatic heterocyclic group include a 5- to 14-membered ring composed of at least one selected from the group consisting of 1 to 3 nitrogen atoms, 1 oxygen atom, and 1 sulfur atom and a carbon atom. And a monocyclic, bicyclic or tricyclic aromatic heterocyclic group. Specific examples of the aromatic heterocyclic group include pyridyl group, quinolinyl group, isoquinolinyl group, indolyl group, pyrrolyl group, furyl group, benzofuryl group, thienyl group, benzothienyl group, isobenzofuranyl group, pyrazolyl group, pyrazinyl group Quinazolinyl group, carbazolyl group, triazinyl group, quinoxalinyl group, imidazolyl group, benzoxazolyl group and the like.

  Examples of the aliphatic heterocyclic group include a 5- to 7-membered ring composed of at least one selected from the group consisting of 1 to 3 nitrogen atoms, 1 oxygen atom, and 1 sulfur atom and a carbon atom. And a monocyclic aliphatic heterocyclic group. Specific examples of the aliphatic heterocyclic group include piperidino group, pyrrolidino group, tetrahydrofuranyl group, morpholinyl group, piperazinyl group, thiomorpholinyl group, imidazolidinyl group, thiazolidinyl group, hexahydropyrimidinyl group and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  As the amino group, for example, dimethylamino group, diethylamino group, diisopropylamino group, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, tert-butylamino group, unsubstituted And the amino group.

  Examples of the alkoxyl group include a methoxyl group, an ethoxyl group, a propoxyl group, a butoxyl group, a phenoxyl group, and a naphthoxy group.

  Examples of the carbamoyl group include a naphthylcarbamoyl group and a phenylcarbamoyl group.

  As an alkoxycarbonyl group, a C2-C10 alkoxycarbonyl group is mentioned, for example.

  As a perfluoroalkyl group, a C1-C6 perfluoroalkyl group is mentioned, for example.

  Examples of the substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, and a tert-butyl group, and an unsaturated double bond such as a vinyl group, an allyl group, an ethynyl group, and a propargyl group. And aliphatic hydrocarbon group, aryl group, heteroaromatic ring group, aliphatic heterocyclic group, halogen atom, amino group, alkoxy group, carbamoyl group and the like.

In the unit represented by the formula (1), R ¹ and R ² are the same, R ³ and R ⁴ are the same, or R ¹ and R ² are the same and R ³ and R ⁴ are preferably the same from the viewpoint of the structural stability and controllability of the resulting helical polymer.

  As the group having a site capable of coordinating with a metal, for example, a group having a phosphorus atom, a nitrogen atom or a sulfur atom is preferable. Specific examples of the group having a site capable of coordinating with a metal include a pyridine ring, a quinoline ring, a group having an oxazoline ring or a thiophene ring, and a bipyridyl group. Examples of the group having a site capable of coordinating with a suitable metal include groups represented by the following formulas (3) to (6).

(In the formula, the position of the bond may be any position of ortho, meta and para.)

(In the formula, the position of the bond may be any position of ortho, meta and para.)

In the formula (5) and the formula (6), R ⁹ and R ¹⁰ may be the same or different, and each independently an aryl group which may have a substituent, having 1 to 8 carbon atoms Examples thereof include a linear or branched alkyl group, a cycloalkyl group, a heteroaromatic ring group, a fatty heterocyclic group, an alkoxy group, an amino group, and a hydroxyl group. A is a direct bond, a linear or branched alkyl group having 1 to 6 carbon atoms, which may have a substituent, an aryl group, a heteroaromatic ring group, an aliphatic heterocyclic group, an oxygen-containing alkyl group, or a nitrogen-containing alkyl group. Etc. Y is an oxygen atom or a sulfur atom.

  Examples of the substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, and a tert-butyl group, and an unsaturated double bond such as a vinyl group, an allyl group, an ethynyl group, and a propargyl group. And aliphatic hydrocarbon group, aryl group, heteroaromatic ring group, aliphatic heterocyclic group, halogen atom, amino group, alkoxy group, carbamoyl group and the like.

  Specific examples of the unit represented by the formula (1) include groups represented by the following formulas (7) to (15). Among these, the group represented by the formula (7) and the group represented by the formula (12) are preferable in that the conformation is easily fixed. In the formulae, Ph represents a phenyl group, and Me represents a methyl group.

  Examples of the coordination mode with the metal include monodentate coordination and bidentate coordination. With bidentate ligands, the reaction efficiency is low, and there are many systems in which an efficient reaction is realized only by a monodentate ligand. In such a case, it is preferable to use a monodentate ligand.

  Examples of the optically active helical polymer of the present invention include homopolymers and copolymers containing the unit represented by the formula (1), and copolymers are preferred.

  As the unit derived from the comonomer of the copolymer component, a unit represented by the following formula (2) is preferable.

In the formula, each of R ^{5 to} R ⁸ independently represents a hydrogen atom, an optionally substituted linear or branched alkyl group, an aliphatic hydrocarbon group having an unsaturated double bond, or a cyclic alkyl group. Selected from the group consisting of aryl group, aromatic heterocyclic group, aliphatic heterocyclic group, halogen atom, cyano group, nitro group, carboxyl group, amino group, alkoxyl group, carbamoyl group, alkoxycarbonyl group and perfluoroalkyl group It is a group. R ^{5 to} R ⁸ may be the same or different, and R ⁵ and R ⁷ , R ⁷ and R ^8, or R ⁸ and R ⁶ may each form a ring.

R ^{5 to} R ⁸ are as described above, and R ⁵ and R ¹ , R ⁶ and R ² , R ⁷ and R ^3, and R ⁸ and R ⁴ are not the same. Therefore, the unit represented by the formula (1) and the unit represented by the formula (2) constituting the copolymer are not the same.

  As a specific example of the unit represented by the formula (2), a unit represented by the following formula (16) and a unit represented by (17) are preferable in that the solubility of the polymer and the control of the winding direction of the helix are excellent. In addition, a unit represented by the following formula (18) is preferable in that synthesis, isolation and identification are easy.

In the unit represented by the formula (2), it is preferable that any group of R ^{5 to} R ⁸ is an alkyl group substituted with sodium sulfonate in terms of imparting water solubility. A typical example thereof is a unit represented by the following formula (19).

In the unit represented by the formula (2), it is preferable that any one of R ^{5 to} R ⁸ has an alkoxyl group in terms of imparting amphiphilicity. A typical example thereof is a unit represented by the following formula (20).

  Among the units represented by the formula (2), a unit having a perfluoro group in the side chain which specifically dissolves in the fluorinated solvent is preferable from the viewpoint of recovery and reuse.

In the formula, Y represents an oxygen atom or a sulfur atom. R ¹¹ and R ¹² are preferably each independently an alkyl group having 1 to 12 carbon atoms. Moreover, it is preferable that m is an integer of 1-12. n is preferably 0 or an integer of 1 to 11. Moreover, it is preferable that the sum of m and n is an integer of 1-12.

In the formula, each of R ¹¹ and R ¹² is preferably independently an alkyl group having 1 to 12 carbon atoms. l is preferably an integer of 1 to 11. m is preferably an integer of 1 to 12. n is preferably 0 or an integer of 1 to 11. Moreover, it is preferable that the sum of m and n is an integer of 2-18.

  In the formula, Me represents a methyl group.

In the formula, R ¹¹ and R ¹² are the same as described above.

In the formula, R ¹¹ , R ¹² and n are the same as described above.

  As a copolymer containing the unit represented by Formula (2), a random copolymer and a block copolymer are mentioned. Of these, block copolymers are preferred.

  At the end of the polymer, the uniformity of the helical structure may be slightly broken. Therefore, in a homopolymer or a diblock polymer, a reaction that occurs in such a disordered portion may lower the selectivity of the catalytic reaction. On the other hand, the triblock copolymer is preferable because the catalyst sites are gathered on the inner side of the polymer and the uniformity of the helical structure in the asymmetric reaction field can be maintained. As a triblock copolymer, both ends of the optically active helical polymer of the unit represented by the formula (1) having a site capable of coordinate bonding with a metal are sandwiched between the optically active helical polymer having a unit represented by the formula (2). Triblock copolymers having a structure are preferred.

  Further, a triblock copolymer having a structure in which the hydrophilic unit represented by the formula (19) and the hydrophobic unit represented by the formula (18) are combined, for example, a block composed of the hydrophilic unit and the hydrophobic unit. A tribook copolymer in which a block consisting of a unit and a block consisting of the hydrophilic unit are combined in this order, a block consisting of the hydrophobic unit, a block consisting of the hydrophilic unit, and a block consisting of the hydrophobic unit Tribook copolymers in which and are bonded in this order are preferable in terms of imparting amphiphilic properties.

  When the optically active helical polymer containing the unit represented by the formula (2) is a copolymer, the unit represented by the formula (2) per 1 mole of the unit represented by the formula (1) having a site capable of coordination with a metal. The amount of is preferably 1 to 40 mol, and more preferably 2 to 20 mol. The amount of the unit represented by the formula (2) per 1 mol of the unit represented by the formula (1) is 40 mol or less from the viewpoint of improving the content of the coordinating moiety per polymer weight and improving the economy and reaction efficiency. From the viewpoint of increasing the solubility of the polymer by preventing the amount of metal coordinated to the polymer chain from becoming too much, suppressing the reduction of stereoselectivity of the reaction due to interference between reaction points, and increasing the solubility of the polymer. It is preferable that it is more than mol.

  The number average molecular weight (hereinafter referred to as Mn) of the optically active helical polymer is preferably 3,000 to 3,000,000. The molecular weight distribution of the optically active helical polymer (hereinafter referred to as Mw / Mn) is arbitrary because it does not have a great influence on the optical yield and the like.

  The optically active helical polymer of the present invention does not exhibit optical activity by itself, but exhibits optical activity when a helical polymer is formed.

  The helical structure in the optically active helical polymer of the present invention is very stable, but there are three factors that affect its stability, namely (i) the 5th and 8th positions of the unit represented by the formula (1). There are bulkiness of substituents, (ii) degree of polymerization (stable as the chain length increases), and (iii) bulkiness of terminal substituents.

  The effect of the terminal substituents is surprisingly great. When both ends are methyl groups, only one end, for example, a 1,1′-binaphthyl-2-diyl group, can be racemized at room temperature. Even when heated to a temperature of about 100 ° C., the polymer is not racemized at all by replacing with a bulky aryl group such as. Also, the more stable the helical structure of the polymer, the less likely it is that the spiral will unwind once formed.

  The optically active helical polymer of the present invention can be obtained, for example, by polymerizing a 1,2-diisocyanobenzene derivative represented by the following formula (21) as a monomer using a polymerization initiator.

In the formula, R ^{1 to} R ⁴ are the same as described above.

  When the optically active helical polymer of the present invention is used as a copolymer, an optically active helical copolymer can be prepared by adding a monomer represented by the following formula (22) to the 1,2-diisocyanobenzene derivative. .

In the formula, R ^{5 to} R ⁸ are the same as described above. R ^{5 to} R ⁸ are the same as R ^{1 to} R ⁴ , respectively, but R ⁵ and R ¹ , R ⁶ and R ² , R ⁷ and R ^3, and R ⁸ and R ⁴ are all the same substituents. It will never be.

  Among the monomers represented by the formula (22), a monomer represented by the following formula (23) is preferable, and a 1,2-diisocyanobenzene derivative represented by the following formula (24) is more preferable.

In the formula, R ¹¹ , R ¹² , Y, m and n are the same as described above.

  In the formula, Me represents a methyl group.

  The polymerization initiator used when polymerizing the monomer is obtained by reacting an aromatic compound or aromatic heterocyclic compound with nickel or a palladium compound in the presence of a ligand.

  The mother nucleus of the aromatic compound or aromatic heterocyclic compound is not particularly limited. Examples thereof include hydrocarbon compounds such as benzene, naphthalene and phenanthrene, and heterocyclic compounds such as pyridine, pyrrole, indole, thiophene, furan, pyrazole, pyrimidine, quinoline and quinoxaline. Of these, benzene and naphthalene are preferred from the viewpoint of easy availability of raw materials and ease of synthesis, structural similarity with the polymerization intermediate, easy isolation of the initiator, and ease of handling. In view of the above, quinoxaline is preferable.

There is no particular limitation on the substituent of the aromatic compound or aromatic heterocyclic compound. Specific examples of the substituent of the aromatic compound or aromatic heterocyclic compound include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkylsulfonyloxy group [RSO ₃ — (R represents an alkyl group). ), For example, TsO (TsO represents tosylate), TfO (TfO represents triflate), etc.], acyloxy groups [RCO ₂ — (R represents an alkyl group), for example, AcO (Ac represents an acetyl group) ), BzO (Bz represents benzoyl), etc.], pseudohalogens such as O = P (OR) ₂ O, metal-containing substituents such as magnesium halide, and the like. Among these, a chlorine atom, a bromine atom, and an iodine atom are preferable from the viewpoint of easy availability and easy preparation of nickel and palladium compounds.

  The aromatic compound or aromatic heterocyclic compound is not particularly limited. Examples of the aromatic compound or aromatic heterocyclic compound include binaphthyl derivatives, biphenyl derivatives, ferrocene derivatives having asymmetric carbon, axial asymmetry or plane asymmetry. Preferable examples of the aromatic compound or the aromatic heterocyclic compound include chiral aromatic compounds. Among them, a compound represented by the following formula (25) and a compound represented by the following (26) are preferable, and the following formula: The compound represented by (27) and the compound represented by the following (28) are more preferred.

In the formula, X is a halogen group, R ^* is an optically active substituent, Ac is an acetyl group, Ph is a phenyl group, tol is a tolyl group, Ar is an aryl group, R and R ^{1 to} R ⁷ are each a hydrogen atom, Optionally substituted linear or branched alkyl group, aliphatic hydrocarbon group having an unsaturated double bond, aryl group, aromatic heterocyclic group, aliphatic heterocyclic group, halogen atom, cyano group, nitro A group selected from the group consisting of a group, a carboxyl group, an amino group, an alkoxyl group and a carbamoyl group, and R ^{1 to} R ⁴ and R ^{5 to} R ⁷ are different from each other.

The nickel or palladium compound used as the polymerization initiator is not particularly limited. Examples of the polymerization initiator include nickel zero-valent complexes such as Ni (cod) ₂ (cod represents 1,5-cyclooctadiene; the same applies hereinafter), NiCl ₂ , NiBr ₂ , Ni (acac) ₂ (acac Represents acetylacetone, the same shall apply hereinafter, such as nickel divalent compounds, Pd (OAc) ₂ (Ac represents an acetyl group, the same shall apply hereinafter), Pd (acac) ₂ , PdCl ₂ , PdCl ₂ (NCCH ₃ ) _2, PdCl ₂ (NCPh) ₂ , Cp (π-allyl) Pd (Cp is cyclopentadienyl, allyl is an allyl group, the same applies hereinafter), Pd (dba) ₂ (dba is dibenzalacetone, the same applies hereinafter) , Pd ₂ (dba) ₃ , Pd (PPh ₃ ) ₄ and other palladium compounds. Of these, Ni (cod) ₂ , Cp (π-allyl) Pd, Pd (dba) ₂ and Pd ₂ (dba) ₃ are preferred.

  The ligand is not particularly limited as long as it can coordinate to nickel or palladium. Examples of the ligand include trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, triarylphosphine, pyridine derivatives, bipyridine derivatives, phenanthroline derivatives, and the like. Of these, trimethylphosphine is preferable.

  Examples of the optically active ligand include optically active tertiary phosphine, optically active diphosphine, optically active carbene, optically active tertiary amine, optically active sulfide, and optically active primary or 2 having active hydrogen capable of deprotonation. Examples thereof include tertiary amines, optically active carboxylic acids, optically active alcohols, optically active thiols and their deprotonated anions.

  In the present invention, it is sufficient that at least one of the aromatic compound, the aromatic heterocyclic compound and the ligand is optically active.

  The synthesis of the polymerization initiator may be performed under basic conditions. In that case, examples of the base to be used include pyridine, trialkylamine, imidazole, t-butoxy potassium, t-butoxy sodium and the like.

  Examples of the solvent for the asymmetric polymerization of the monomer 1,2-diisocyanobenzene derivative include tetrahydrofuran (hereinafter referred to as THF), 1,4-dioxane, toluene, benzene, xylene, diethyl ether, Examples include hexane, isopropyl alcohol, dichloromethane, chloroform, and the like. These may be used alone or in combination of two or more. Of the solvents, THF is preferred.

  The polymerization initiator reacts an aromatic compound or aromatic heterocyclic compound with a nickel or palladium compound and a 1,2-diisocyanobenzene derivative represented by the formula (21) in the presence of a ligand. Can be obtained. Note that at least one of the aromatic compound, the aromatic heterocyclic compound, and the ligand has an optically active site.

  When synthesizing an optically active helical polymer containing a unit having a site capable of coordinating with a metal, if the monomer having a unit having a site capable of coordinating with a metal is bulky and polymerization does not proceed, coordination is performed. It is also possible to give a site capable of coordinate binding by polymerizing a monomer having a precursor of a site capable of site binding.

  After completion of the polymerization reaction, a polymerization terminator may be added to the reaction system. Examples of the polymerization terminator include alkyl lithium, aryl lithium, diisobutyl aluminum hydride, metal zinc, metal aluminum, lithium aluminum hydride, sodium borohydride and the like.

  The reaction temperature when producing the optically active helical polymer is preferably -20 to 60 ° C. The reaction temperature is preferably −20 ° C. or higher from the viewpoint of increasing the reaction rate and obtaining a sufficiently high molecular weight helical polymer, and is 60 ° C. or lower from the viewpoint of narrowing the molecular weight distribution and improving the excess in the helical direction. It is preferable.

  As a method for producing the optically active helical polymer, an aromatic compound or aromatic heterocyclic compound, nickel or palladium compound and a ligand are reacted, and then a polymerization initiator as a reaction product is purified. , 2-diisocyanobenzene derivative may be polymerized, and after reacting the ligand with an aromatic compound or aromatic heterocyclic compound and nickel or palladium compound, 1,2-diisocyano without purification The benzene derivative may be polymerized and the product purified thereafter, or the aromatic compound or aromatic heterocyclic compound, nickel or palladium compound, ligand and 1,2-diisocyanobenzene derivative may be combined. May be mixed to carry out the polymerization reaction.

  As the optically active aryl group bonded to nickel or palladium, an aryl moiety other than the halogen group in the aromatic compound or aromatic heterocyclic compound can be applied as it is, and among them, a group represented by the following formula (29) And a group represented by the formula (30) is preferable, and a group represented by the following formula (31) and a group represented by the formula (32) are more preferable.

In the formula, R ^* represents an optically active substituent, Ac represents an acetyl group, Ph represents a phenyl group, and tol represents a tolyl group.

  The optically active group bonded to nickel or palladium is not limited to the optically active aryl group, and may be an optically active group among the ligands.

  Further, it is preferable that a halogen group or a pseudohalogen group is further bonded to nickel or palladium. Examples of the halogen group or pseudohalogen group include the halogen and pseudohalogen.

  The optically active helical polymer is synthesized by aromatizing asymmetric living polymerization of a 1,2-diisocyanobenzene derivative using an organic nickel complex or an organic palladium complex as an initiator.

This asymmetric living polymerization proceeds by a continuous insertion reaction of an isocyano group into a CM bond. The optically active aryl group (Ar ^* ) possessed by the initiator moves away from the growth end as the polymerization proceeds. Nevertheless, the helix is completely controlled because the helical structure of the helical polymer is extremely rigid. The helical structure is formed in the initial stage of about a trimer, but at this point, the left and right helices can still be unwound, and a thermodynamically stable helix is formed by the steric effect of Ar ^* . As the degree of polymerization increases, unwinding becomes less likely and the helical structure is formed kinetically along the direction of the helix that has already been formed.

  Examples of the metal that coordinates and bonds with the site capable of coordinating bonding in the optically active helical polymer include elements of Groups 4 to 16 and lanthanide elements (f block elements) in the 4th to 6th periods. Among these, palladium, nickel, platinum, rhodium, ruthenium, iridium, gold, silver, copper, iron and cobalt are preferable.

The metal compound used when the optically active helical polymer and the metal are coordinated and bonded includes Cp, cod, acac, π-allyl, (p-C ₃ H ₅ ), NCCH ₃ , NCPH, dba, PPh ₃ , chlorine atom It is preferable to use a metal complex having a ligand such as a halogen atom such as a bromine atom. Specific examples of the metal compound include Ni (cod) ₂ , NiCl ₂ , NiBr ₂ , Ni (acac) ₂ , Cp (π-allyl) Pd (II), [PdCl (p-allyl)] ₂ , Pd ( OAc) ₂ , Pd (acac) ₂ , PdCl ₂ , PdCl ₂ (NCCH ₃ ) _2, PdCl ₂ (NCPh) ₂ , Pd (dba) ₂ , Pd ₂ (dba) ₃ , Pd (PPh ₃ ) ₄ , Pt ( cod) ₂ , Pt (PPh ₃ ) ₄ , Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ , [Rh (cod) Cl] ₂ , [Rh (nbd) Cl] ₂ (nbd means norbornadiene) , RhCl (PPh ₃ ) ₃ , Rh (acac) (CO) ₂ , Rh (acac) (CH ₂ ═CH ₂ ) ₂ , RuCl ₃ , Ru (acac) ₃ , [RuCl ₂ (CO) ₃ ] ₂ , Ru ₃ (CO) _12, RuH _{2 PPh 3) 4, Co (acac} ) 2, Co 2 (CO) 8, [Au (CN-C 6 H 11) 2] BF 4, Cu (OTf) 2, (CuOTf) 2, AgOTf, [IrCl (cod )] ₂ , Cu (CH ₃ CN) ₄ PF ₆ , Fe (acac) ₃ , FeCl ₃ , RuCl ₂ (cod), RuCl ₂ (nbd), [RuCl ₂ (ethylene) ₂ ] _{2 and the} like. Among these, Cp (π-allyl) Pd (II) is preferable in terms of high complex formation efficiency.

  The optically active helical polymer of the present invention is derived from the rigidity of optical isomer separation materials such as chiral columns and chiral separation membranes, optical materials such as nonlinear optical materials, chiral polymer materials, chiral polymer catalysts, and helical polymers. It can be applied to fields and products that utilize the physical strength retaining component of a living body such as skin, the rigid rod shape and the helical structure.

  The chiral polymer catalyst using the optically active helical polymer of the present invention can be obtained by a coordinate bond between a site capable of coordinate bonding in the optically active helical polymer and a metal. As the metal that forms a coordinate bond, the same metal as the metal that forms a coordinate bond with the site capable of coordinate bond can be used.

Examples of the reaction using the chiral polymer catalyst of the present invention include hydrosilylation reaction, silylboration reaction, allylic nucleophilic substitution reaction and the like, but the present invention is not limited to such examples. Absent. More specifically, the reaction using the chiral polymer catalyst of the present invention includes addition to alkenes, allenes and 1,3-dienes as shown in the formulas (33), (34) and (35). Reaction. In the formulas (33), (34) and (35), Poly-cat ^* is a chiral polymer catalyst using the optically active helical polymer of the present invention, and Pt, Pd and Ni in parentheses are arranged. It is a metal that is coordinated to a site that can coordinate.

  The reaction temperature in the asymmetric synthesis using the catalyst of the present invention is preferably −80 to 150 ° C., more preferably −60 to 80 ° C., further preferably −40 to 50 ° C., although it depends on the reaction conditions. ˜35 ° C. is particularly preferred. The reaction temperature is preferably 150 ° C. or lower from the viewpoint of increasing the optical yield by racemization of the polymer, and is preferably −80 ° C. or higher from the viewpoint of dissolving the polymer and accelerating the reaction.

  In addition, in order to develop a new function different from the above function, a functional helical polymer resulting from the molecular structure of the substituent is created by introducing a substituent having other functionality into the side chain portion. be able to. It is possible to elucidate the principle of life function expression through the functional helical polymer created in this way, and to construct functional materials with conductivity, light emission, liquid crystal, photoresponsiveness, ferroelectricity, etc. it can. Examples of such a substituent include azobenzene, 1,2-diarylethene, polythiophene, porphyrin and the like.

  In addition, a helical structure in the desired direction is constructed from a polymer having steric regularity, and substituents, organic compounds, inorganic compounds, fullerenes, enzymes, etc. consisting of any group of compounds can be freely set along the helical axis. It can also be expected to create a functional helical polymer arranged in a series.

  In addition, not only a single helical polymer, but also an assembly of helical polymers, if precise sequence control becomes possible, “molecular recognition ability”, “catalysis”, “information function (self-replication and self-replication)” It is expected to be applied as a new chiral material such as chiral discriminating materials, sensors, membranes, and liquid crystal materials.

  Therefore, according to the present invention, not only will it lead to the creation of innovative functional materials that surpass the performance of existing polymers, but it will also contribute greatly to the advancement of chiral technology, which is important in medical and pharmaceutical development. There is expected.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 (Production of optically active helical polymer)
1. polymerization

A dried Schlenk reaction tube was charged with 102 mg (100 μmol) of a polymerization initiator (a) and 301 mg (1.0 mmol) of 10 equivalents of monomer (b), and the reaction vessel was purged with nitrogen, and then placed in an ice bath and 50 ml of THF was added and stirred. . The reaction temperature was allowed to rise slowly to room temperature. After 13 hours, it was confirmed by analytical GPC that the monomer had been completely consumed, and then the solvent amount was concentrated to about half in the glove box, and 42 mg (99 μmol) of 1 equivalent of phosphorus side chain-containing monomer (c) was added. A solution dissolved in 2.5 ml of THF was added. After 5 hours, it was confirmed that the monomer (c) was completely consumed, and 300 mg (1.0 mmol) of the monomer (b) was added. After confirming that the monomer (b) was completely consumed after 17 hours, 38 mg (1.0 mmol) of NaBH ₄ was added and stirring was continued as it was. After 1 hour, water was added and extracted with CHCl ₃ . The organic phase was washed twice with water and dried over MgSO ₄ . After filtration, the solvent was distilled off with an evaporator and vacuum-dried to obtain a quinoxaline copolymer (d). The polymer portion was separated and purified by preparative GPC. The yield of the obtained polymer was 679.1 mg, and the yield was 98%.

¹ H-NMR (CDCl ₃ ) δ 0.89 (br s 6nH), 1.59 (br s 4nH), 2.34 (br s 6nH), 3.46 (br s 6nH), 4.58 (br s), 6.4-8.2 (br m) ; ³¹ P-NMR (CDCl ₃ ) δ 29.53 (br s)

2. Reduction of phosphine oxide

Polymer (d) was placed in a dry Youngcock-equipped reaction tube, and after nitrogen substitution, 7.5 ml of THF and 7.5 ml of toluene were added, and 343 μl (2.00 mmol) of P (OEt) ₃ and 1 ml (10 mmol) of trichlorosilane were added. Was added and sealed, and then heated to 80 ° C. After 24 hours, the product was taken out from the oil bath and allowed to cool to room temperature. Then, CHCl ₃ was added to dilute the solution, and the mixture was poured into a 5N NaOH aqueous solution containing ice. After extraction three times with CHCl ₃ , the organic phase was washed with saturated aqueous NaHCO ₃ solution. The obtained brown suspension was No. Filter through 500 Celite. The filtrate was further washed with water and dried over MgSO ₄ . No. The mixture was filtered through 500 Celite, and the solvent was distilled off with an evaporator, followed by vacuum drying. Polymer (e) was obtained by GPC. The yield of the obtained polymer was 409.3 mg, and the yield was 59%. Mn was 3500 and Mw / Mn was 1.63.

¹ H-NMR (CDCl ₃ ) δ 0.89 (br s 6nH), 1.58 (br s 4nH), 2.33 (br s 6nH), 3.45 (br s 6nH), 4.57 (br s), 6.3-8.2 (br m) ; ³¹ P-NMR (CDCl ₃ ) δ -15.39 (br s)

Example 2 (Production of chiral polymer catalyst)
1. Catalyst preparation

18.5 μl (1.0 μmol) of 5.4 × 10 ⁻² M [PdCl (π-allyl)] ₂ solution and 28.3 mg of polymer (e) (phosphine content 4 μmol) in a reaction tube with a Youngcock in a glove box And the solvent was distilled off under vacuum.

2. Synthesis of optically active 1-phenylethanol by asymmetric hydrosilylation-oxidation of styrene

Synthesis of 2-1.1-trichlorosilyl-1-phenylethane 210 mg (2.0 mmol) of styrene was added to the catalyst prepared by the above operation under a nitrogen atmosphere. After cooling well in an ice bath, 0.3 ml (3 mmol) of trichlorosilane was added. After stirring for 14 hours in an ice bath and confirming the consumption of styrene by GC, excess trichlorosilane was removed with a diaphragm pump, and colorless transparent 1-trichlorosilyl-1-phenylethane was obtained by Kugel distillation. Obtained. The yield was 457.2 mg, and the yield was 95%.

2-2. Synthesis of optically active 1-phenylethanol by oxidation 1-trichlorosilyl-1-phenyl dissolved in 20 ml of THF was placed in a 200 ml eggplant flask with 639.6 mg (11.9 mmol) of KF, 1.6561 g (16.5 mmol) of KHCO ₃ and 20 ml of MeOH. 452.5 mg (1.9 mmol) of ethane was added. To this mixture, 1.3 ml of 30% by weight hydrogen peroxide water was added and stirred at room temperature for 15 hours. A saturated aqueous Na ₂ S ₂ O ₃ solution was added in an ice bath, and the mixture was stirred for 1 hour, extracted three times with ether, and the organic phase was dried over MgSO ₄ . The solvent was distilled off with an evaporator and purified by Kugel distillation to obtain 1-phenylethanol. The optical purity of this product was 69% ee. The optical purity was determined by chiral column chromatography (DAICEL OD-H hexane: isopropyl alcohol = 9: 1).

Example 2 (Asymmetric hydrosilylation of various substituted styrenes)

18.5 μl (1.0 μmol) of 5.4 × 10 ⁻² M [PdCl (π-allyl)] ₂ solution and 28.3 mg of polymer (e) (phosphine content 4 μmol) in a reaction tube with a Youngcock under a nitrogen atmosphere And the solvent was distilled off under vacuum. To the catalyst thus prepared, 2.0 mmol of the styrene derivative shown in Table 1 was added under a nitrogen atmosphere. After cooling well in an ice bath, 0.3 ml (3 mmol) of trichlorosilane was added. Stir in the ice bath for the time listed in Table 1, and after confirming the consumption of styrene by GC (gas chromatography), excess trichlorosilane is removed under reduced pressure and distilled under reduced pressure. A hydrosilylation product was obtained.

  The yield, optical purity and oxidation yield (%) of the obtained asymmetric hydrosilylation-substituted styrene are also shown in Table 1.

Example 3 (silyl boronation of allene)

Under a nitrogen atmosphere, 22.4 mg of polymer (e) was placed in a vial, 29.7 mg (0.24 mmol) of 1-cyclohexyl-1,2-propadiene and 2- (dimethylphenylsilyl) -4,4,5,5- After adding 52.4 mg (0.20 mmol) of tetramethyl-1,3,2-dioxaborolane, 171 μl (1.2 × 10 ⁻² M, 2.0 μmol) of a toluene solution of Cp (π-allyl) Pd was added. It was. After stirring for 36 hours at room temperature, 3-cyclohexyl-3- (dimethylphenylsilyl) -2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1 was obtained by distillation. -76.4 mg of propene was obtained. The optical purity of this product was determined to be 46% ee by analysis by chiral column chromatography (DAICEL OD-H hexane 100%).

Example 4 (Hydrosilylation of norbornene)

Under a nitrogen atmosphere, put 50.3 μl (9.9 × 10 ⁻³ M, 0.5 μmol) of a toluene solution of [PdCl (π-allyl)] ₂ and 18.9 mg of polymer (e) in a reaction tube with a Youngcock. The solvent was removed under vacuum. To the catalyst thus prepared, 94.7 mg (1.0 mmol) of norbornene was added in a glove box, and after cooling in an ice bath, 0.15 ml (1.5 mmol) of trichlorosilane was added. It was. After stirring at 0 ° C. for 64 hours, excess trichlorosilane was removed under reduced pressure. 2-Trichlorosilyl [2.2.1] heptane was obtained by distillation under reduced pressure. The yield was 199.0 mg, and the yield was 86%.

In order to determine the optical purity of the product, the following conversion reaction was performed. An eggplant flask was charged with 288.8 mg (5.0 mmol) of KFCO and 739.0 mg (7.4 mmol) of KHCO _{3, and} 188.7 mg (0.82 mmol) of 2-trichlorosilyl [2.2.1] heptane was added to MeOH (methanol). It was dissolved in 8 ml of THF (1: 1) solution and added. To this, 1.1 ml of 30% by weight hydrogen peroxide solution was added and stirred at room temperature for 90 hours. After immersing in an ice bath, a saturated aqueous Na ₂ S ₂ O ₃ solution was added and stirred for 30 minutes, followed by extraction four times with ether, and the organic phase was dried over MgSO ₄ . The solvent was distilled off with an evaporator and exo-norbornol was obtained by Kugel distillation.

  Further, 9.0 mg (80 μmol) of the obtained exo-norbornol was placed in a vial, and 3,5-dinitrophenyl isocyanate 25.2 mg (0.12 mmol), toluene 0.9 ml and pyridine 0.45 ml were placed in a glove box. And heated to 60 ° C. After stirring for 2 hours, the mixture was filtered through Celite (No. 535), and the solvent was distilled off with an evaporator. Silica gel thin layer chromatography (hexane: ethyl acetate = 3: 1) gave exo-2-bicyclo [2.2.1] heptyl 3,5-dinitrophenylcarbamate.

  The optical purity of the obtained 3,5-dinitrophenylcarbamate exo-2-bicyclo [2.2.1] heptyl product was 38% ee. For the determination of optical purity, chiral column chromatography (Sumichiral OA-4500 hexane: 1,2-dichloroethane: ethanol = 50: 10: 1) was used.

Example 5 (Asymmetric alkylation reaction of allyl ester)

Under a nitrogen atmosphere, 45.1 mg of polymer (e) (phosphine content 4.8 μmol) and 100 μl of a solution of [PdCl (π-allyl)] ₂ in methylene chloride (2.0 × 10 ⁻² M, 2.0 μmol) were placed in a vial. Then, 1.1 ml of methylene chloride was added and stirred at room temperature for 1 hour. This solution was transferred to another vial containing 50.5 mg (0.20 mmol) of (±)-(E) -1,3-diphenyl-2-propenylacetate and stirred for 5 minutes. 1 μl (0.60 mmol), 146.8 μl (0.60 mmol) of N, O-bis (trimethylsilyl) acetamide and 1 mg (0.01 mmol) of potassium acetate were added. After stirring at room temperature for 45 hours, saturated aqueous NH ₄ Cl solution was added and the reaction mixture was shaken. Extracted with chloroform and the organic phase was dried over MgSO ₄ . By filtering through Celite (No. 500) and purifying by silica gel column chromatography (hexane: ethyl acetate = 5: 1), dimethyl (E)-(1,3-diphenylallyl) malonate was converted to dimethyl malonate. As a mixture with a yield of 98%.

  The optical purity of this product was 0.8% ee. This optical purity was determined by chiral column chromatography (DAICEL OB-H hexane: isopropyl alcohol = 98: 2).

Example 6 (Hydrosilylation of cyclopentadiene)

Under a nitrogen atmosphere, in a reaction tube equipped with a Youngcock, polymer (e) 18.8 mg (phosphine content 2 μmol) and [PdCl (π-allyl)] ₂ in toluene solution 50.3 μl (9.9 × 10 ⁻³ M, 0. 5 μmol), and the solvent was distilled off under vacuum. After adding 63.7 mg (0.96 mmol) of cyclopentadiene in the glove box to the catalyst thus prepared, 1.2 ml (1.2 mmol) of trichlorosilane was added. After stirring at room temperature for 39 hours, excess trichlorosilane was removed under reduced pressure, and 3-trichlorosilylcyclopentene was obtained by distillation. The yield was 104.2 mg, and the yield was 54%.

Under a nitrogen atmosphere, 42.0 mg (0.40 mmol) of benzaldehyde was taken, and 95.9 mg (0.48 mmol) of 3-trichlorosilylcyclopentene obtained earlier was dissolved in 2 ml of DMF and added. After stirring for 2 hours under ice cooling, the reaction was quenched by adding saturated aqueous NaHCO ₃ solution. Extraction with ether, washing with water and brine, the organic phase was dried over Na ₂ SO ₄ . Α-2-cyclopenten-1-ylbenzenemethanol was obtained by silica gel thin layer chromatography (hexane: ethyl acetate = 4: 1). The optical purity of this product was 0.8% ee.

Example 7 (Diborylation of allene)

Under a nitrogen atmosphere, 5.8 mg (10 μmol) of Pd (dba) ₂ was placed in a vial, and 84.7 mg of polymer (e) (phosphine content 12 μmol) was dissolved in 0.5 ml of toluene and then stirred at room temperature for 1 hour. . Here, cyclohexyl-1,2-propadiene and 4,4,4 ′, 4 ′, 5,5,5 ′, 5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane were sequentially added to toluene ( The total amount was dissolved in 1 ml) and added. After stirring at room temperature for 12 hours, the solvent was distilled off with an evaporator. Purification by silica gel column chromatography (hexane: ethyl acetate = 50: 1) and 2- (1-cyclohexyl-1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) ) -2-propen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The yield was 42.1 mg, and the yield was 61%.

42.1 mg (0.11 mmol) of the obtained product was placed in a Schlenk tube, and 12.4 mg (0.12 mmol) of benzaldehyde dissolved in 0.3 ml of toluene was added under a nitrogen atmosphere. After stirring at room temperature for 24 hours, 0.3 ml each of tetrahydrofuran and 3N NaOH aqueous solution was added, and after cooling by immersion in an ice bath, 0.3 ml of 30 wt% hydrogen peroxide solution was added dropwise. After stirring for 5 hours at room temperature, 0.3 ml each of a saturated aqueous Na ₂ S ₂ O ₃ solution and a 1N aqueous NaOH solution were added, and the mixture was further stirred for 30 minutes. Extracted twice with 3 ml of ethyl acetate and the organic phase was dried over Na ₂ SO ₄ . Purification by silica gel thin layer chromatography (hexane: ethyl acetate = 5: 1) gave 1-cyclohexyl-4-hydroxy-4-phenyl-2-butanone. The optical purity of this product was 8% ee. For determination of optical purity, chiral column chromatography (DAICEL OD-H hexane: isopropyl alcohol = 95: 5) was used.

Example 8 (Synthesis of block polymers having various degrees of polymerization)
A dried Schlenk reaction tube was charged with 102 mg (0.1 mmol) of the polymerization initiator (a) and 301 mg (1.0 mmol) of the monomer (b) to 903 mg (3.0 mmol), and the reaction vessel was purged with nitrogen, and then an ice bath And THF was added and stirred.

  The amount of THF added was adjusted so that the monomer (b) was 0.2 mol / L. The reaction temperature was allowed to rise slowly to room temperature. After 13 hours, it was confirmed by analytical GPC that the monomer was completely consumed. Then, the solvent amount was concentrated under reduced pressure to about half, and 42 mg (0.1 mmol, a block polymer synthesis containing one monomer unit containing a phosphorus moiety) or 84 mg (0.2 mmol, phosphorus moiety) containing a phosphorus side chain-containing monomer (c) A block polymer synthesis containing 2 monomer units containing 1) in 2.5 ml THF was added.

After 5 hours, it was confirmed that the monomer (c) was completely consumed, and 301 mg (1.0 mmol) to 903 mg (3.0 mmol) of the monomer (b) were added. After confirming that the monomer (b) was completely consumed after 17 hours, 38 mg (1.0 mmol) of NaBH ₄ was added and stirring was continued as it was. After 1 hour, water was added and extracted with CHCl ₃ . The organic phase was washed twice with water and dried over MgSO ₄ .

  After filtration, the solvent was distilled off with an evaporator and vacuum-dried to obtain a quinoxaline copolymer (d). The polymer portion was separated and purified by preparative GPC. The obtained quinoxaline copolymer (d) was reduced in the same manner as in “2. Reduction of phosphine oxide” to obtain a polymer (e).

The following monomers (f) and (g) are used in place of the monomer (c), and block polymers Q ₁₀ TP ₁ Q ₁₀ , Q ₁₀ TP ₂ Q ₁₀ and Q ₁₀ FP in which the phosphorus-containing site is different from the polymer (e) ₁ Q ₁₀ was synthesized. Note that TP in the abbreviation indicates a monomer unit derived from the monomer (f), and FP indicates a monomer unit derived from (g).

Example 9 (Synthesis of block polymer having repetitive structure of non-coordinating site and coordination site)
A dried reaction tube with Youngcock was charged with 20.5 mg (20 μmol) of the polymerization initiator (a) and 5 ml of THF, and was removed from the glove box.

  After immersing in an ice bath, 60.1 mg (0.2 mmol) of 10 equivalents of monomer (b) dissolved in 2 ml of THF was added. The reaction temperature was allowed to rise slowly to room temperature. It was confirmed by TLC that the monomer (b) was completely consumed, and 1 equivalent of the phosphorus-containing monomer (c) was dissolved in 2 ml of THF at room temperature and added. After stirring at room temperature and confirming that the phosphorus-containing monomer was completely consumed by analytical GPC, the reaction solution was concentrated to about 5 ml under reduced pressure.

After immersion in an ice bath, 60.1 mg (0.2 mmol) of 10 equivalents of monomer (b) dissolved in 2 ml of THF was added. The operation of adding monomer (b) and monomer (c) was repeated two more times in the same manner as above, and then an excess amount (40 equivalents) of NaBH ₄ was added. After stirring at room temperature for 1 hour, water was added and extracted with CHCl ₃ . The organic phase was washed once with saturated brine and water and dried over MgSO ₄ . After filtration, the solvent was distilled off with an evaporator and vacuum-dried to obtain a quinoxaline polymer. The polymer portion was separated and purified by preparative GPC. The obtained quinoxaline copolymer was reduced in the same manner as in “2. Reduction of phosphine oxide”.

Example 10 (Random polymer synthesis)
A dried reaction tube with Youngcock was charged with 10.4 mg (10.2 μmol) of the polymerization initiator (a) and 3 ml of THF, and 30.2 mg (101 μmol) of 10 equivalents of the monomer (b) dissolved in 3 ml of THF was added. It was removed from the glove box and stirred at room temperature.

After confirmation by TLC that the monomer was completely consumed after 26 hours, it was immersed in an ice bath and 24.5 mg (50 μmol) of 5 equivalents of phosphorus-containing monomer (c) and 286 mg (0. 95 mmol) was dissolved in 10 ml of THF and added. After stirring at 0 ° C. for 83 hours, it was confirmed by TLC that the monomer had been completely consumed, and 38.2 mg (1.0 mmol) of NaBH ₄ was added.

After stirring at room temperature for 1 hour, water was added and extracted with CHCl ₃ . The organic phase was washed once with saturated brine and water and dried over MgSO ₄ . After filtration, the solvent was distilled off with an evaporator and vacuum-dried to obtain a quinoxaline polymer. The polymer portion was separated and purified by preparative GPC.

  The obtained quinoxaline copolymer was reduced in the same manner as in “2. Reduction of phosphine oxide”.

  The results of Examples 8-10 are summarized below.

Q ₁₀ ^m P ₁ Q ₁₀
Yield 85%. Mn = 3447, Mw / Mn = 1.27. ¹ H-NMR (CDCl ₃ ) δ0.89 (br s 6nH), 1.59 (br s 4nH), 2.33 (br s 6nH), 3.46 (br s 6nH), 4.57 (br s), 6.4-8.1 (br m); ³¹ P-NMR (CDCl ₃ ) δ29.29 (br s)

Q ₁₀ ^m P ₁ Q ₁₀
Yield 74%. Mn = 3783, Mw / Mn = 1.211. ¹ H-NMR (CDCl ₃ ) δ0.94 (br s 6nH), 1.64 (br s 4nH), 2.39 (br s 6nH), 3.51 (br s 6nH), 4.62 (br s), 6.4-8.2 (br m); ³¹ P-NMR (CDCl ₃ ) δ-15.77 (br s)

Q ₃₀ ^m PO ₁ Q ₁₀
Yield 87%. Mn = 9874, Mw / Mn = 1.46. 1 H-NMR (CDCl 3) δ0.94 (br s 6nH), 1.63 (br s 4nH), 2.38 (br s 6nH), 3.49 (br s 6nH), 4.61 (br s), 6.2-8.3 (br m); ³¹ P-NMR (CDCl ₃ ) δ29.34 (br s)

Q ₃₀ ^m P ₁ Q ₁₀
Yield 60%. Mn = 6660, Mw / Mn = 1.79. ¹ H-NMR (CDCl ₃ ) δ0.92 (br s 6nH), 1.62 (br s 4nH), 2.37 (br s 6nH), 3.49 (br s 6nH), 4.62 (br s), 6.4-8.1 (br m); ³¹ P-NMR (CDCl ₃ ) δ-14.78 (br s)

Q ₁₀ ^m PO ₁ Q ₃₀
Yield: 69%. Mn = 8879, Mw / Mn = 1.51. 1 H-NMR (CDCl 3) δ0.92 (br s 6nH), 1.61 (br s 4nH), 2.37 (br s 6nH), 3.48 (br s 6nH), 4.62 (br s), 6.2-8.1 (br m); ³¹ P-NMR (CDCl ₃ ) δ29.24 (br s)

Q ₁₀ ^m P ₁ Q ₃₀
Yield 52%. Mn = 8774, Mw / Mn = 1.58. 1 H-NMR (CDCl 3) δ0.92 (br s 6nH), 1.61 (br s 4nH), 2.37 (br s 6nH), 3. 48 (br s 6nH), 4.60 (br s), 6.4-8.1 (br m); ³¹ P-NMR (CDCl ₃ ) δ-15.58 (br s)

Q ₁₀ ^m PO _0.9 Q ₁₀
Yield 79%. Mn = 3487, Mw / Mn = 1.44. ¹ H-NMR (CDCl ₃ ) δ0.91 (br s 6nH), 1.61 (br s 4nH), 2.36 (br s 6nH), 3.48 (br s 6nH), 4.60 (br s), 6.3-8.1 (br m); ³¹ P-NMR (CDCl ₃ ) δ29.77 (br s), 28.90 (br s)

Q ₁₀ ^m P _0.9 Q ₁₀
Yield 58%. Mn = 3901, Mw / Mn = 1.54. ¹ H-NMR (CDCl ₃ ) δ0.89 (br s 6nH), 1.60 (br s 4nH), 2.35 (br s 6nH), 3.46 (br s 6nH), 4.59 (br s), 6.4-8.1 (br m); ³¹ P-NMR (CDCl ₃ ) δ-15.23 (br s)

Q ₁₀ ^m PO _0.5 Q ₁₀
83% yield. Mn = 3456, Mw / Mn = 1.54. 1 H-NMR (CDCl 3) δ0.93 (br s 6nH), 1.63 (br s 4nH), 2.38 (br s 6nH), 3.50 (br s 6nH), 4.62 (br s), 6.4-8.1 (br m); ³¹ P-NMR (CDCl ₃ ) δ29.72 (br s)

Q ₁₀ ^m P _0.5 Q ₁₀
Yield 64%. Mn = 4899, Mw / Mn = 1.31. ¹ H-NMR (CDCl ₃ ) δ0.91 (br s 6nH), 1.61 (br s 4nH), 2.37 (br s 6nH), 3.48 (br s 6nH), 4.60 (br s), 6.4-8.1 (br m); ³¹ P-NMR (CDCl ₃ ) δ-15.17 (br s)

Q ₁₀ ^m PO ₂ Q ₁₀
Yield 86%. Mn = 3852, Mw / Mn = 1.31. ¹ H-NMR (CDCl ₃ ) δ0.92 (br s 6nH), 1.62 (br s 4nH), 2.37 (br s 6nH), 3.49 (br s 6nH), 4.62 (br s), 6.3-8.2 (br m); ³¹ P-NMR (CDCl ₃ ) δ29.76 (br s)

Q ₁₀ ^m P ₂ Q ₁₀
Yield 60%. Mn = 4986, Mw / Mn = 1.34. ¹ H-NMR (CDCl ₃ ) δ0.90 (br s 6nH), 1.60 (br s 4nH), 2.36 (br s 6nH), 3.47 (br s 6nH), 4.59 (br s), 6.3-8.1 (br m); ³¹ P-NMR (CDCl ₃ ) δ-15.53 (br s)

Q ₁₀ ( ^m PO ₁ Q ₁₀ ) ₃ block yield 76%. Mn = 9012, Mw / Mn = 1.52. ¹ H-NMR (CDCl ₃ ) δ0.93 (br s 6nH), 1.62 (br s 4nH), 2.38 (br s 6nH), 3.49 (br s 6nH), 4.61 (br s), 6.2-8.2 (br m); ³¹ P-NMR (CDCl ₃ ) δ29.75 (br s)

Q ₁₀ ( ^m P ₁ Q ₁₀ ) ₃ block yield 57%. Mn = 8191, Mw / Mn = 1.66. ¹ H-NMR (CDCl ₃ ) δ0.93 (br s 6nH), 1.62 (br s 4nH), 2.38 (br s 6nH), 3.49 (br s 6nH), 4.60 (br s), 6.4-8.2 (br m); ³¹ P-NMR (CDCl ₃ ) δ-15.17 (br s)

^{_{Q 10 [m PO 5 Q 95}} ] Random yield 79%. Mn = 24449, Mw / Mn = 1.76. ¹ H-NMR (CDCl ₃ ) δ0.92 (br s 6nH), 1.62 (br s 4nH), 2.37 (br s 6nH), 3.48 (br s 6nH), 4.61 ( br s), 6.1-8.2 (br m); ³¹ P-NMR (CDCl ₃ ) δ28.74 (br s)

Q ₁₀ [ ^m P ₅ Q ₉₅ ] Random yield 46%. Mn = 12556, Mw / Mn = 2.91. ¹ H-NMR (CDCl ₃ ) δ0.91 (br s 6nH), 1.61 (br s 4nH), 2.36 (br s 6nH), 3.47 (br s 6nH), 4.60 (br s), 6.3-8.2 (br m); ³¹ P-NMR (CDCl ₃ ) δ-15.16 (br s)

Q ₁₀ TPO ₁ Q ₁₀
Yield 83%. Mn = 3448, Mw / Mn = 1.531. ¹ H-NMR (CDCl ₃ ) δ0.91 (br s 6nH), 1.62 (br s 4nH), 2.37 (br s 6nH), 3.49 (br s 6nH), 4.61 (br s), 6.3-8.2 (br m); ³¹ P-NMR (CDCl ₃ ) δ28-30 (br m)

Q ₁₀ TP ₁ Q ₁₀ (602)
Yield 51%. Mn = 3798, Mw / Mn = 1.41. ¹ H-NMR (CDCl ₃ ) δ0.90 (br s 6nH), 1.61 (br s 4nH), 2.37 (br s 6nH), 3.48 (br s 6nH), 4.60 (br s), 6.3-8.2 (br m); ³¹ P-NMR (CDCl ₃ ) δ 16.2 to 14.4 (br m)

Q ₁₀ TPO ₂ Q ₁₀
Yield 76%. Mn = 3391, Mw / Mn = 2.44.1 ¹ H-NMR (CDCl ₃ ) δ 0.91 (br s 6nH), 1.60 (br s 4nH), 2.37 (br s 6nH), 3.48 (br s 6nH), 4.60 (br s), 6.3-8.2 (br m); ³¹ P-NMR (CDCl ₃ ) δ27-30 (br m)

Q ₁₀ TP ₂ Q ₁₀
Yield 39%. Mn = 3897, Mw / Mn = 1.55. ¹ H-NMR (CDCl ₃ ) δ0.89 (br s 6nH), 1.59 (br s 4nH), 2.34 (br s 6nH), 3.46 (br s 6nH), 4.59 (br s), 6.0-8.2 (br m); ³¹ P-NMR (CDCl ₃ ) δ 16.0 to 14.4 (br m)

Q ₁₀ FPO ₁ Q ₁₀
Yield 89%. Mn = 3455, Mw / Mn = 2.22.1 ¹ H-NMR (CDCl ₃ ) δ0.95 (br s 6nH), 1.65 (br s 4nH), 2.40 (br s 6nH), 3.51 (br s 6nH), 4.63 (br s), 6.3-8.4 (br m); ³¹ P-NMR (CDCl ₃ ) δ22.17 (br s), 24.42 (br s)

Q ₁₀ FP ₁ Q ₁₀
Yield 41%. Mn = 3962, Mw / Mn = 1.44. ¹ H-NMR (CDCl ₃ ) δ0.89 (br s 6nH), 1.60 (br s 4nH), 2.36 (br s 6nH), 3.47 (br s 6nH), 4.59 (br s), 6.5-8.1 (br m); ³¹ P-NMR (CDCl ₃ ) δ-14.11 (br s)

  The optically active helical polymer of the present invention has a defect-free helical structure, the spiral winding direction (right-handed, left-handed) is completely controlled, and side chain modification, molecular weight control, copolymer synthesis, etc. are easily performed. In addition, since the side chain has a group having a site capable of coordinating with a metal, various optical functions can be imparted.

  In addition, the present invention produces a large number of asymmetric reaction fields from a catalytic amount of an optically active source by synthesizing a chiral monomer by asymmetric polymerization of all the ligand sites and by asymmetric polymerization of achiral monomers. And a catalytic reaction having high enantioselectivity and a large turnover number in each asymmetric reaction field.

  Furthermore, by using the chiral polymer catalyst of the present invention, in addition to the feature of the polymer catalyst that the separation and recovery of the catalyst after the reaction is remarkably facilitated, the chiral asymmetry formed by asymmetric polymerization is chiral. Since it is used as a reaction field, the synthesis of an optically active substance can be carried out easily and reliably.

Claims (4)

Following formula (1):

(In the formula, R ^{1 to} R ⁴ are each independently a hydrogen atom, an optionally substituted linear or branched alkyl group, an aliphatic hydrocarbon group having an unsaturated double bond, or cyclic alkyl. Group, aryl group, aromatic heterocyclic group, aliphatic heterocyclic group, halogen atom, cyano group, nitro group, carboxyl group, amino group, alkoxyl group, carbamoyl group, alkoxycarbonyl group and perfluoroalkyl group R ^{1 to} R ⁴ are the same or different and R ¹ and R ³ , R ³ and R ⁴ or R ⁴ are groups having at least one site capable of coordinating with a metal. And R ² may each form a ring.)
And a group having a site capable of coordinating with the metal is represented by the formula (3):

(In the formula, the position of the bond may be any position of ortho, meta and para.)
A group represented by formula (4):

(In the formula, the position of the bond may be any position of ortho, meta and para.)
A group represented by formula (5):

(Wherein R ⁹ and R ¹⁰ may be the same or different and each independently represents an aryl group, a linear or branched alkyl group having 1 to 8 carbon atoms, a cyclo A group selected from the group consisting of an alkyl group, a heteroaromatic group, a fatty heterocyclic group, an alkoxy group, an amino group and a hydroxyl group, and A is a direct bond or may have a substituent; It is a group selected from the group consisting of straight or branched alkyl groups having 1 to 6 carbon atoms, aryl groups, heteroaromatic ring groups, aliphatic heterocyclic groups, oxygen-containing alkyl groups and nitrogen-containing alkyl groups.)
Or a group represented by formula (6):

(In the formula, R ⁹ , R ¹⁰ and A are the same as described above. Y is an oxygen atom or a sulfur atom.)
An optically active helical polymer which is a group represented by: The optically active helical polymer according to claim 1, further comprising a unit represented by the following formula (2) as a repeating unit .

(In the formula, each of R ^{5 to} R ⁸ independently represents a hydrogen atom, an optionally substituted linear or branched alkyl group, an aliphatic hydrocarbon group having an unsaturated double bond, or cyclic alkyl. Group, aryl group, aromatic heterocyclic group, aliphatic heterocyclic group, halogen atom, cyano group, nitro group, carboxyl group, amino group, alkoxyl group, carbamoyl group, alkoxycarbonyl group and perfluoroalkyl group R ^{5 to} R ⁸ may be the same or different, and R ⁵ and R ⁷ , R ⁷ and R ^8, or R ⁸ and R ⁶ may each form a ring. However, each of R ^{5 to} R ⁸ is a group that does not have a site capable of coordinating with a metal.) Coordinated metal in at least one coordination possible binding sites, claim 2 in which the metal is at least one selected from the group consisting of elements and lanthanides having 4 to 16 Group 4 to 6 cycles The optically active helical polymer described in 1. A chiral polymer catalyst for use in an asymmetric reaction, wherein the optically active helical polymer according to claim 3 is used.