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WO2020059824A1 - Composé polyène conjugué contenant du bore, procédé de production associé et procédé de production d'un composé polyène conjugué - Google Patents

Composé polyène conjugué contenant du bore, procédé de production associé et procédé de production d'un composé polyène conjugué Download PDF

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Publication number
WO2020059824A1
WO2020059824A1 PCT/JP2019/036830 JP2019036830W WO2020059824A1 WO 2020059824 A1 WO2020059824 A1 WO 2020059824A1 JP 2019036830 W JP2019036830 W JP 2019036830W WO 2020059824 A1 WO2020059824 A1 WO 2020059824A1
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boron
group
conjugated polyene
compound
raw material
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Japanese (ja)
Inventor
平野　雅文
小峰　伸之
小織 清田
歩実 倉持
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Tokyo University of Agriculture and Technology NUC
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Tokyo University of Agriculture and Technology NUC
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Priority to CN201980061406.1A priority Critical patent/CN112714767A/zh
Priority to JP2020548619A priority patent/JP7389490B2/ja
Publication of WO2020059824A1 publication Critical patent/WO2020059824A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/21—Alkatrienes; Alkatetraenes; Other alkapolyenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
    • C07C15/44—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic the hydrocarbon substituent containing a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
    • C07C69/618—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety having unsaturation outside the six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a boron-containing conjugated polyene compound, a method for producing the same, and a method for producing a conjugated polyene compound.
  • a conjugated polyene skeleton in which carbon-carbon double bonds and single bonds are alternately repeated is a structure often found in physiologically active substances such as antifungal drugs and vitamins. Also, various applications of the conjugated polyene skeleton to electronic material applications have been studied. For this reason, methods for introducing a conjugated polyene skeleton into a target compound have been studied.
  • Non-Patent Document 1 discloses that a polyenylboronic acid having a boronic acid group on a conjugated polyene skeleton is formed using a haloalkenylboronic acid protected by a specific protecting group, and the polyenylboronic acid is subjected to a cross-coupling reaction.
  • a method using enylboronic acid for synthesizing a physiologically active substance is disclosed.
  • An object of the present invention is to provide a novel boron-containing conjugated polyene compound having a conjugated polyene skeleton and a boron-containing group bonded thereto and useful for the synthesis of a physiologically active substance, an electronic material, and the like, and a method for producing the same. And Another object of the present invention is to provide a method for producing a conjugated polyene compound using the above-mentioned boron-containing conjugated polyene compound.
  • One aspect of the present invention relates to a method for producing a boron-containing conjugated polyene compound.
  • This production method comprises a first raw material compound having a carbon-carbon triple bond and a conjugate having a 1,3-butadiene-4,4-diyl group and containing two carbon-carbon double bonds in the group.
  • a second raw material compound having a di (or poly) ene skeleton is reacted in the presence of a metal catalyst to form a boron-containing conjugated polyene compound having a conjugated polyene skeleton containing three or more carbon-carbon double bonds.
  • At least one of the first raw material compound and the second raw material compound is boron-containing bonded to a carbon atom constituting the triple bond or the conjugated di (or poly) ene skeleton.
  • the boron-containing conjugated polyene compound has a boron-containing group bonded to a carbon atom constituting the conjugated polyene skeleton.
  • a boron-containing conjugated polyene compound having a conjugated polyene skeleton and a boron-containing group bonded to the conjugated polyene skeleton can be easily obtained.
  • the conjugated polyene skeleton can be easily introduced into the target compound by a reaction (for example, a cross-coupling reaction) starting from the boron-containing group.
  • the above-mentioned boron-containing conjugated polyene compound can also be applied to electronic materials and the like as a ⁇ -conjugated compound having a boron-containing group.
  • the first raw material compound may be a compound represented by the following formula (1-1), and the second raw material compound may be represented by the following formula (1-2-1)
  • the boron-containing conjugated polyene compound may be a compound represented by the following formula (1-3-1).
  • B 1 represents a boron-containing group
  • R 1 represents a monovalent group.
  • n represents an integer of 0 or more
  • R 2 and R 3 each independently represent a hydrogen atom or a monovalent group.
  • n is 1 or more
  • a plurality of R 2 may be the same or different from each other.
  • a plurality of R 3 may be the same or different from each other.
  • R 2 together, R 3 together, and, R 2 and R 3 may be bonded to each other to form a ring.
  • B 1 , R 1 , n, R 2 and R 3 have the same meanings as described above. Note that the wavy line indicates that the double bond bonded to the wavy line may be either cis or trans.
  • At least one of R 3 in the formula (1-2-1) may be a boron-containing group.
  • a boron-containing conjugated polyene compound having boron-containing groups at both ends of the conjugated polyene skeleton is obtained.
  • This boron-containing conjugated polyene compound can be suitably used for producing a polymer compound by cross-coupling polymerization, in addition to the above-mentioned applications.
  • the first raw material compound may be a compound represented by the following formula (1-1), and the second raw material compound may be a compound represented by the following formula (1-2-2).
  • the boron-containing conjugated polyene compound may be a compound represented by the following formula (1-3-2).
  • a boron-containing conjugated polyene compound having boron-containing groups at both ends of the conjugated polyene skeleton is obtained.
  • This boron-containing conjugated polyene compound can be suitably used for producing a polymer compound by cross-coupling polymerization, in addition to the above-mentioned applications.
  • B 1 represents a boron-containing group
  • R 1 represents a monovalent group.
  • n 1 represents an integer of 0 or more, n 2 represents 0 or 1, and R 2 represents a hydrogen atom or a monovalent group.
  • n 1 represents 1 or more, a plurality of R 2 may be the same or different from each other.
  • R 2 's may combine with each other to form a ring.
  • B 1 , R 1 , n 1 , n 2 and R 2 each have the same meaning as described above.
  • Two B 1 represents may be the same or different from each other.
  • two R 1 s may be the same or different.
  • the wavy line indicates that the double bond bonded to the wavy line may be either cis or trans.
  • the R 1 may be a silyl group
  • the production method may include replacing the R 1 in the boron-containing conjugated polyene compound with a hydrogen atom to form a second boron-containing conjugated polyene compound.
  • the method may further include a step of obtaining a compound.
  • the first raw material compound may be a compound represented by the following formula (2-1), and the second raw material compound may be represented by the following formula (2-2).
  • the boron-containing conjugated polyene compound may be a compound represented by the following formula (2-3).
  • R 4 and R 5 each independently represent a monovalent group.
  • m represents an integer of 0 or more, and R 6 and R 7 each independently represent a hydrogen atom or a monovalent group.
  • at least one of the two R 7 is a boron-containing group.
  • m is 1 or more, a plurality of R 6 may be the same or different from each other. Further, two R 7 s may be the same or different from each other.
  • R 6 to each other, R 7 together, and, R 6 and R 7 may be bonded to each other to form a ring.
  • R 4 , R 5 , m, R 6 and R 7 are the same as defined above. Note that the wavy line indicates that the double bond bonded to the wavy line may be either cis or trans.
  • the value of the Hammett substituent constant ⁇ p of R 4 may be larger than the value of the Hammett substituent constant ⁇ p of R 5 .
  • the above R 5 may be a silyl group, and at this time, the above production method may be such that the above R 5 in the above boron-containing conjugated polyene compound is replaced with a hydrogen atom to form a second boron-containing conjugated polyene compound.
  • the method may further include a step of obtaining a compound.
  • the metal catalyst may include at least one selected from the group consisting of ruthenium (Ru), rhodium (Rh), cobalt (Co), and nickel (Ni).
  • the metal catalyst may be a ruthenium catalyst.
  • the ruthenium catalyst may form zero-valent ruthenium in the reaction system.
  • Another aspect of the present invention relates to a boron-containing conjugated polyene compound represented by the following formula (1-3-1A), the following formula (1-3-2A), or the following formula (2-3A).
  • B 1 represents a boron-containing group
  • R 11 represents a hydrogen atom or a monovalent group
  • n represents an integer of 0 or more
  • R 2 and R 3 are each independently Represents a hydrogen atom or a monovalent group.
  • n represents 1 or more
  • a plurality of R 2 may be the same or different from each other.
  • a plurality of R 3 may be the same or different from each other.
  • R 2 together, R 3 together, and, R 2 and R 3 may be bonded to each other to form a ring.
  • B 1 represents a boron-containing group
  • R 11 represents a hydrogen atom or a monovalent group
  • n 1 represents an integer of 0 or more
  • n 2 represents 0 or 1.
  • R 2 represents a hydrogen atom or a monovalent group. However, when n 1 is 1 or more, n 2 is 1.
  • a plurality of R 2 may be the same or different from each other.
  • R 2 's may combine with each other to form a ring.
  • two B 1 represents may be the same or different from each other.
  • R 4 represents a monovalent group
  • R 15 represents a hydrogen atom or a monovalent group
  • m represents an integer of 0 or more
  • R 6 and R 7 each independently represent It represents a hydrogen atom or a monovalent group.
  • at least one of the two R 7 is a boron-containing group.
  • m is 1 or more
  • a plurality of R 6 may be the same or different from each other.
  • two R 7 s may be the same or different from each other.
  • R 6 to each other, R 7 together, and, R 6 and R 7 may be bonded to each other to form a ring.
  • the wavy line indicates that the double bond bonded to the wavy line may be either cis or trans.
  • Still another aspect of the present invention is a method for producing a boron-containing conjugated polyene compound, the first step of obtaining a reaction solution containing the boron-containing conjugated polyene compound, and the reaction solution, a coupling reaction catalyst, And a second step of performing a coupling reaction by adding a third raw material compound having a reactive group capable of performing a coupling reaction with the boron-containing group.
  • the reactive group may be a halogeno group.
  • the first step may be a step of forming the boron-containing conjugated polyene compound in a reaction system in the presence of the metal catalyst, and the second step may be performed in the reaction system. And the step of adding the coupling reaction catalyst and the third raw material compound.
  • a novel boron-containing conjugated polyene compound having a conjugated polyene skeleton and a boron-containing group bonded thereto and useful for the synthesis of a physiologically active substance, an electronic material, and the like, and a method for producing the same are provided.
  • a method for producing a conjugated polyene compound using the above-mentioned boron-containing conjugated polyene compound is provided.
  • the method for producing a boron-containing conjugated polyene compound according to the present embodiment includes a first raw material compound having a carbon-carbon triple bond and a 1,3-butadiene-4,4-diyl group. Reacting a second raw material compound having a conjugated di (or poly) ene skeleton containing two carbon-carbon double bonds in the presence of a metal catalyst to form a conjugate containing three or more carbon-carbon double bonds.
  • at least one of the first raw material compound and the second raw material compound has a triple bond or a boron-containing group bonded to a carbon atom constituting a conjugated di (or poly) ene skeleton.
  • the boron-containing conjugated polyene compound has a boron-containing group bonded to a carbon atom constituting the conjugated polyene skeleton.
  • a boron-containing conjugated polyene compound having a conjugated polyene skeleton and a boron-containing group bonded to the conjugated polyene skeleton can be easily obtained.
  • a conjugated polyene skeleton can be easily introduced into a target compound by a reaction (for example, a cross-coupling reaction) starting from a boron-containing group.
  • the boron-containing conjugated polyene compound can also be applied to electronic materials and the like as a ⁇ -conjugated compound having a boron-containing group.
  • the boron-containing group may be an atomic group remaining after removing one functional group on the boron atom in the boron compound. That is, the boron-containing group may be a monovalent group that binds to a binding target via a boron atom.
  • the boron-containing group is not particularly limited, and can be appropriately selected within a range in which the reaction between the first raw material compound and the second raw material compound proceeds.
  • Examples of the boron-containing group include a boryl group, a borono group, a borate group, and a derivative group thereof.
  • Boryl group a group represented by -BH 2.
  • a diorganoboril group can be mentioned.
  • the diorganoboryl group may be, for example, a group represented by —B (R 21 ) 2 .
  • R 21 represents a monovalent group.
  • the two R 21 s may be the same or different, and may combine with each other to form a ring with a boron atom.
  • R 21 may be, for example, a monovalent organic group, and may be an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • the alkyl group for R 21 may be linear, branched, or cyclic.
  • the carbon number of the alkyl group in R 21 is not particularly limited, and may be, for example, 1 to 8.
  • the aryl group for R 21 represents the remaining atomic group obtained by removing one hydrogen atom on an aromatic ring from an aromatic compound.
  • the aromatic ring of the aromatic compound may be a single ring, a condensed ring, or a heterocyclic ring.
  • Examples of the aromatic compound include benzene, naphthalene, furan, pyrrole, thiophene, pyridine and the like.
  • the substituent which the alkyl group and the aryl group in R 21 may have is not particularly limited as long as the reaction between the first raw material compound and the second raw material compound proceeds.
  • Examples of the substituent include a hydroxy group, a carbonyl group, a formyl group, a hydroxycarbonyl group, an ester group, an amino group, and a thiol group.
  • diorganoboryl group examples include, for example, a diphenylboryl group, a dicyclohexyl group, a bicyclo [3.3.1] nonane-1,5-diyl group, and a disiamyl group.
  • the borono group indicates a group represented by -B (OH) 2 .
  • Examples of the borono group derivative group include, for example, a boronate group, a protected borono group, and the like.
  • the boronate group may be, for example, a group represented by —B (OR 22 ) 2 .
  • R 22 represents a monovalent group. Two R 22 s may be the same or different, and may combine with each other to form a ring together with a boron atom and an oxygen atom.
  • R 22 may be, for example, a monovalent organic group, and may be an alkyl group which may have a substituent or an aryl group which may have a substituent. Examples of the alkyl group and the aryl group in R 22 and the substituents that these may have include the same as the alkyl group and the aryl group in R 21 and the substituents that these may have.
  • boronate group examples include, for example, a diisopropylboronate group and a ditert-butylboronate group.
  • the protected borono group is not particularly limited, and may be, for example, a group protected by a method known as protection of a borono group.
  • the protected borono group for example, a group formed by a reaction between a bifunctional compound such as a diol, a diamine, a dicarboxylic acid and the like and a borono group is exemplified.
  • a bifunctional compound such as a diol, a diamine, a dicarboxylic acid and the like
  • a borono group is exemplified.
  • the diol include pinacol, neopentyl glycol, catechol, pinanediol, 1,2-dicyclohexyldiol, and the like.
  • the diamine include 1,8-diaminonaphthalene.
  • the dicarboxylic acid include N-methyliminodiacetic acid.
  • Examples of the protected borono group include a borate group such as a triol borate group. Triol borate groups are formed by the reaction of a triol with a borono group. Examples of the triol include trimethylolethane (1,1,1-tris (hydroxymethyl) ethane).
  • the counter cation of the borate group is not particularly limited, and may be, for example, a sodium ion (Na + ), a potassium ion (K + ), an organophosphonium ion (PR 4 + ), or the like.
  • borate group examples include a trifluoroborate group (—BF 3 ⁇ ) in addition to the above-described triol borate group.
  • the counter cation of the borate group is not particularly limited, and may be, for example, a sodium ion (Na + ), a potassium ion (K + ), an organophosphonium ion (PR 4 + ), or the like.
  • the metal catalyst is a catalyst capable of forming a boron-containing conjugated polyene compound by reacting a first raw material compound with a second raw material compound, that is, a carbon-carbon triple bond and a 1,3-butadiene-4,4-diyl group. Any catalyst can be used as long as it can form a conjugated triene skeleton by the above reaction.
  • a catalyst containing at least one selected from the group consisting of ruthenium (Ru), rhodium (Rh), cobalt (Co) and nickel (Ni) is preferable, and a ruthenium catalyst is more preferable.
  • the ruthenium catalyst can form zero-valent ruthenium (Ru (0)) in the reaction system from the viewpoint that the first raw material compound and the second raw material compound can be efficiently reacted by a reaction mechanism described later.
  • Ru (0) zero-valent ruthenium
  • it is a catalyst. That is, the polyene forming step may be a step of reacting the first raw material compound and the second raw material compound in the presence of Ru (0).
  • reaction mechanism of the polyene forming step An example of the reaction mechanism of the polyene forming step will be described below.
  • a compound represented by the following formula (1-1) is used as a first raw material compound, butadiene is used as a second raw material compound, and [(naphthalene) (1,5-cyclooctadiene) is used as a metal catalyst. ) Ruthenium (0)] is used to explain the reaction mechanism, but the present invention is not limited thereto. Further, the reaction mechanism of the polyene forming step is not limited to the following example.
  • naphthalene is dissociated from the ruthenium complex, and the first raw material compound and the second raw material compound are respectively coordinated on ruthenium (0) (A above).
  • the above-mentioned B is formed by an oxidative coupling reaction
  • the above-mentioned C is formed by ⁇ -hydride elimination.
  • reductive elimination forms the above-mentioned D in which a conjugated triene is coordinated on ruthenium.
  • butadiene since butadiene has two reaction points, another molecule of the first raw material compound reacts by the same mechanism to form the above-described E to which the conjugated tetraene is coordinated.
  • the conjugated tetraene is dissociated from the ruthenium to obtain a boron-containing conjugated polyene compound.
  • the boron-containing conjugated polyene compound dissociates from ruthenium at the stage of D.
  • Examples of the catalyst capable of forming Ru (0) in the reaction system include a zero-valent ruthenium complex having Ru (0) and a divalent ruthenium complex having Ru (II).
  • Examples of the zero-valent ruthenium complex include [(naphthalene) (1,5-cyclooctadiene) ruthenium (0)] and [(butadiene) (1,5-cyclooctadiene) (acetonitrile) ruthenium (0)]. Is mentioned.
  • divalent ruthenium complex examples include [bis (acetylacetonato) (1,5-cyclooctadiene) ruthenium (II)] and [tetrachlorodi (anisole) bruthenium].
  • the divalent ruthenium complex may be reduced in the reaction system to form Ru (0).
  • the divalent ruthenium complex may be reduced by a reaction with a reaction substrate (a first raw material compound and / or a second raw material compound), may be reduced by a reaction between ruthenium complexes, and may be combined with a separately added reducing agent. May be reduced.
  • the reducing agent include butyl lithium, lithium aluminum hydride, sodium naphthalene, a combination of sodium carbonate and isopropyl alcohol, and the like.
  • the type of the ruthenium catalyst is not limited to those described above, and may be any catalyst capable of forming a metallacycle.
  • the ruthenium catalyst may be a catalyst that forms tetravalent ruthenium (Ru (IV)) when forming a metallacycle. That is, the ruthenium catalyst may be a catalyst capable of forming a metallacycle containing tetravalent ruthenium (Ru (IV)) in the reaction system.
  • a rhodium catalyst, a cobalt catalyst, a nickel catalyst, or the like can be used as the metal catalyst.
  • a catalyst capable of forming monovalent rhodium (Rh (I)) in a reaction system is preferable.
  • examples of such a catalyst include a monovalent rhodium complex having Rh (I) and a trivalent rhodium complex having Rh (III).
  • the trivalent rhodium complex may be used in combination with a reducing agent.
  • the reducing agent those similar to the above can be exemplified.
  • a catalyst capable of forming monovalent cobalt (Co (I)) or zero-valent cobalt (Co (0)) in the reaction system is preferable.
  • examples of such a catalyst include a divalent cobalt complex having Co (II).
  • the divalent cobalt complex may be used in combination with a reducing agent.
  • the reducing agent those similar to the above can be exemplified.
  • a catalyst capable of forming zero-valent nickel (Ni (0)) in the reaction system is preferable.
  • examples of such a catalyst include a zero-valent nickel complex having Ni (0) and a divalent nickel complex having Ni (II).
  • the divalent nickel complex may be used in combination with a reducing agent.
  • the reducing agent those similar to the above can be exemplified. Further, as the reducing agent, zinc or the like can be suitably used.
  • the amount of the metal catalyst is not particularly limited, and may be, for example, 0.1 mol% or more, preferably 1 mol% or more, more preferably 5 mol% or more, based on the first raw material compound.
  • the amount of the metal catalyst may be, for example, 30 mol% or less, preferably 20 mol% or less, more preferably 15 mol% or less, based on the first raw material compound.
  • the reaction between the first raw material compound and the second raw material compound may be performed without a solvent or may be performed in an organic solvent.
  • the type of the organic solvent is not particularly limited as long as the solvent can dissolve the first raw material compound and the second raw material compound.
  • the organic solvent include, for example, diethyl ether, tetrahydrofuran, acetone, hexane, benzene, toluene, dichloromethane, dimethyl sulfoxide, and the like, from the viewpoint that it is difficult to inhibit the reaction between the first raw material compound and the second raw material compound. Tetrahydrofuran, benzene, toluene and the like are preferred.
  • the amount of the organic solvent is not particularly limited, and may be, for example, 100 parts by mass or more, preferably 1000 parts by mass or more with respect to the total of 100 parts by mass of the first raw material compound and the second raw material compound. It may be 100,000 parts by mass or less, preferably 10,000 parts by mass or less.
  • the reaction temperature is not particularly limited, and may be, for example, 0 to 100 ° C. or room temperature.
  • the reaction time is not particularly limited, and may be appropriately adjusted depending on the type of the reaction substrate and the catalyst, the desired yield, and the like.
  • the reaction time may be, for example, 0.1 to 72 hours, preferably 1 to 24 hours.
  • the first raw material compound is a compound represented by the following formula (1-1) (hereinafter, also referred to as compound (1-1)), and the second raw material compound is And a compound represented by (1-2-1) (hereinafter, also referred to as compound (1-2-1)).
  • a compound represented by the following formula (1-3-1) (hereinafter, compound (1-3-1) ) Can be obtained.
  • B 1 represents a boron-containing group
  • R 1 represents a monovalent group
  • n represents an integer of 0 or more
  • R 2 and R 3 each independently represent a hydrogen atom or a monovalent group.
  • n is 1 or more
  • a plurality of R 2 may be the same or different from each other.
  • a plurality of R 3 may be the same or different from each other.
  • R 2 together, R 3 together, and, R 2 and R 3 may be bonded to each other to form a ring.
  • the compound represented by the formula (1-3-1) is a compound represented by the following formula (1-3-1a), a compound represented by the following formula (1-3-1b), or a compound represented by the following formula (1-3-1b). May be a mixture of In the first embodiment, among the following compounds, a large amount of the compound represented by the formula (1-3-1a) tends to be obtained.
  • the monovalent group for R 1 is not particularly limited and may be appropriately selected within a range in which the reaction between compound (1-1) and compound (1-2-1) proceeds.
  • the monovalent group in R 1 may be, for example, a monovalent organic group.
  • R 1 may be, for example, an alkyl group which may have a substituent, an aryl group which may have a substituent, a boron-containing group, a silyl group, or the like.
  • the alkyl group for R 1 may be linear, branched or cyclic.
  • the number of carbon atoms of the alkyl group in R 1 is not particularly limited, and may be, for example, 1 to 8.
  • the aryl group in R 1 represents an atomic group obtained by removing one hydrogen atom on an aromatic ring from an aromatic compound.
  • the aromatic ring of the aromatic compound may be a single ring, a condensed ring, or a heterocyclic ring. Examples of the aromatic compound include benzene, naphthalene, thiophene, and the like.
  • the substituent which the alkyl group and the aryl group in R 1 may have is not particularly limited as long as the reaction between the first raw material compound and the second raw material compound proceeds.
  • the substituent include an aryl group, an alkyloxy group, an aryloxy group, a hydroxyl group, a formyl group, a carbonyl group, an amino group, a halogeno group, and the like.
  • the silyl group for R 1 may be a group represented by —Si (R 31 ) 3 .
  • R 31 represents a monovalent group. Three R 31 may be the same or different, may form a ring together with silicon atoms linked to each other.
  • R 31 may be, for example, a monovalent organic group, and may be an alkyl group which may have a substituent or an aryl group which may have a substituent. Examples of the alkyl group and the aryl group in R 31 and the substituents that these may have include the same alkyl group, aryl group and the substituents that the above-mentioned R 21 may have.
  • R 1 is a boron-containing group
  • a boron-containing conjugated polyene compound having a plurality of boron-containing groups bonded to the carbon atoms constituting the conjugated polyene skeleton can be obtained.
  • R 1 when R 1 is a hydrogen atom, the reaction between compound (1-1) and compound (1-2-1) hardly proceeds.
  • R 1 is a silyl group
  • the reactivity between the compound (1-1) and the compound (1-2-1) is good, and the compound (1-3-1) can be obtained regioselectively.
  • a desilylation reaction a boron-containing conjugated polyene compound in which R 1 in compound (1-3-1) has been substituted with a hydrogen atom can be obtained.
  • R 2 when R 2 is a hydrogen atom, a conjugated polyene skeleton having no substituent in the side chain can be formed.
  • the desilylation reaction is not particularly limited, and a known method may be applied.
  • the desilylation reaction can be performed using tetra-n-butylammonium fluoride (TBAF) as a reactant. If the reaction does not proceed easily, a catalytic amount of copper (I) iodide may be added.
  • TBAF tetra-n-butylammonium fluoride
  • the value of the substituent constant sigma p of Hammett may be a smaller group than the value of the substituent constant sigma p of Hammett of B 1.
  • the reaction tends to proceed easily so that the substituent (B 1 ) having a larger value of the substituent constant ⁇ p is located at the end of the conjugated polyene skeleton.
  • N is an integer of 0 or more, and the upper limit is not particularly limited.
  • n may be, for example, from 0 to 8, and preferably from 0 to 2.
  • the monovalent group for R 2 is not particularly limited, and can be appropriately selected as long as the reaction between compound (1-1) and compound (1-2-1) proceeds.
  • the monovalent group for R 2 may be, for example, a monovalent organic group or a halogeno group.
  • the halogeno group for R 2 may be a fluoro group (—F), a chloro group (—Cl), a bromo group (—Br) or an iodo group (—I), preferably a fluoro group (—F) or a chloro group. (—Cl) or a bromo group (—Br).
  • alkyl group and the aryl group in R 2 may be the same as the above-mentioned alkyl group, aryl group and the substituents that R 21 may have. .
  • R 41 represents a hydrogen atom or a monovalent group.
  • R 41 may be, for example, a hydrogen atom or a monovalent organic group, and may be a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • R 42 represents a hydrogen atom or a monovalent group.
  • R 42 may be, for example, a hydrogen atom or a monovalent organic group, and may be a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, It may be an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • Examples of the alkyl group and the aryl group in R 41 and R 42 and the substituents that these may have include the same as the above-described alkyl group and aryl group in R 21 and the substituents that these may have. .
  • the monovalent group for R 3 is not particularly limited, and can be appropriately selected within a range in which the reaction between the compound (1-1) and the compound (1-2-1) proceeds.
  • the monovalent group for R 3 may be, for example, a monovalent organic group or a halogeno group.
  • R 3 the same group as each group in R 2 described above can be exemplified.
  • R 2 and R 3 are boron-containing groups
  • a boron-containing conjugated polyene compound having a plurality of boron-containing groups bonded to carbon atoms constituting the conjugated polyene skeleton can be obtained.
  • R 3 is a boron-containing group
  • a boron-containing conjugated polyene compound having a boron-containing group at both ends of a conjugated polyene skeleton can be obtained.
  • Such a boron-containing conjugated polyene compound can be suitably used for producing a polymer compound by cross-coupling polymerization and the like.
  • the first raw material compound is a compound represented by the formula (1-1) (compound (1-1)), and the second raw material compound is a compound represented by the following formula (1-2-2) ) (Hereinafter, also referred to as compound (1-2-2)).
  • compound (1-2-2) has two reaction points with compound (1-1). Therefore, in the second embodiment, a compound represented by the following formula (1-3-2) having at least two boron-containing groups derived from the compound (1-1) (hereinafter, referred to as compound (1-3-2) ) Can be obtained.
  • B 1 represents a boron-containing group
  • R 1 represents a monovalent group
  • n 1 represents an integer of 0 or more
  • n 2 represents 0 or 1
  • R 2 represents a hydrogen atom or a monovalent group.
  • n 1 is 1 or more
  • a plurality of R 2 may be the same or different from each other.
  • n 1 is 1 or more
  • n 2 is 1.
  • R 2 's may combine with each other to form a ring.
  • B 1 , R 1 , n 1 , n 2 and R 2 have the same meanings as above.
  • Two B 1 represents may be the same or different from each other.
  • two R 1 s may be the same or different.
  • the wavy line indicates that the double bond bonded to the wavy line may be either cis or trans. That is, the compound represented by the formula (1-3-2) includes a compound represented by the following formula (1-3-2a), a compound represented by the following formula (1-3-2b), and a compound represented by the following formula ( It may be a compound represented by 1-3-2c), a compound represented by the following formula (1-3-2d), or a mixture thereof.
  • the compound represented by the formula (1-3-2a) tends to be most frequently obtained.
  • R 1 in the formula (1-1) may be the same as R 1 in the formula (1-1) in the first embodiment.
  • R 2 in the formula (1-2-2) may be the same as R 2 in the formula (1-2-1) in the first embodiment.
  • n 1 is an integer of 0 or more, the upper limit thereof is not particularly limited. n 1 may be, for example, from 0 to 8, and preferably from 0 to 1.
  • n 1 When n 1 is 0, n 2 is 0 or 1, and when n is 1 or more, n 2 is 1.
  • the first raw material compound is a compound represented by the following formula (2-1), and the second raw material compound is a compound represented by the following formula (2-2).
  • a compound represented by the following formula (2-3) (hereinafter, also referred to as compound (2-3)). Can be obtained.
  • R 4 and R 5 each independently represent a monovalent group.
  • m represents an integer of 0 or more, and R 6 and R 7 each independently represent a hydrogen atom or a monovalent group. However, at least one of the two R 7 is a boron-containing group.
  • a plurality of R 6 may be the same or different from each other. Further, two R 7 s may be the same or different from each other. R 6 to each other, R 7 together, and, R 6 and R 7 may be bonded to each other to form a ring.
  • R 4 , R 5 , m, R 6 and R 7 have the same meanings as above.
  • the wavy line indicates that the double bond bonded to the wavy line may be either cis or trans. That is, the compound represented by the formula (2-3) may be a compound represented by the following formula (2-3a), a compound represented by the following formula (2-3b), or a mixture thereof. .
  • a large amount of the compound represented by the formula (2-3a) tends to be obtained.
  • the monovalent group in R 4 and R 5 is not particularly limited, and can be appropriately selected as long as the reaction between the compound (2-1) and the compound (2-2) proceeds.
  • Examples of the monovalent group for R 4 and R 5 include the same groups as those for R 1 described above.
  • the value of Hammett's substituent constant ⁇ p for R 4 is greater than the value of Hammett's substituent constant ⁇ p for R 5 .
  • the reaction tends to proceed easily so that the substituent (R 4 ) having a larger value of the substituent constant ⁇ p is located at the end of the conjugated polyene skeleton.
  • M is an integer of 0 or more, and the upper limit is not particularly limited. m may be, for example, from 0 to 8, and preferably from 0 to 2.
  • the monovalent group for R 6 is not particularly limited and can be appropriately selected within a range in which the reaction between compound (2-1) and compound (2-2) proceeds.
  • Examples of R 6 include the same groups as those of R 2 described above.
  • the monovalent group for R 7 is not particularly limited and may be appropriately selected within a range in which the reaction between compound (2-1) and compound (2-2) proceeds.
  • Examples of R 7 include the same groups as those of R 3 described above. However, at least one of the two R 7 is a boron-containing group.
  • the boron-containing conjugated polyene compound according to the present embodiment is a compound manufactured by the above-described manufacturing method, and includes a conjugated polyene skeleton containing three or more carbon-carbon double bonds, and a carbon atom constituting the conjugated polyene skeleton. And a boron-containing group bonded to
  • the boron-containing conjugated polyene compound according to the first embodiment is a compound represented by the following formula (1-3-1A).
  • R 11 represents a hydrogen atom or a monovalent group, and examples of the monovalent group in R 11 include the same groups as those described above for R 1 .
  • the compound in which R 11 is a hydrogen atom can be obtained, for example, by reacting a compound (1-1) in which R 1 is a silyl group with a compound (1-2-1), and then desilylating the silyl group in R 1 . It can be produced by substituting a hydrogen atom by a reaction.
  • the boron-containing conjugated polyene compound according to the second embodiment is a compound represented by the following formula (1-3-2A).
  • B 1, n 1, n 2 and R 2 have the same meanings as B 1, n 1, n 2 and R 2 in the above formula (1-3-2).
  • R 11 represents a hydrogen atom or a monovalent group, and examples of the monovalent group in R 11 include the same groups as those described above for R 1 .
  • the compound in which R 11 is a hydrogen atom can be obtained, for example, by reacting a compound (1-1) in which R 1 is a silyl group with a compound (1-2-2) and then desilylating the silyl group in R 1 It can be produced by substituting a hydrogen atom by a reaction.
  • the boron-containing conjugated polyene compound according to the third embodiment is a compound represented by the following formula (2-3A).
  • R 4, m , R 6 and R 7 have the same meanings as R 4, m, R 6 and R 7 in the above formula (2-3).
  • R 15 represents a hydrogen atom or a monovalent group, and examples of the monovalent group in R 15 include the same groups as those described above for R 5 .
  • the compound in which R 15 is a hydrogen atom can be obtained, for example, by reacting the compound (2-1) in which R 5 is a silyl group with the compound (2-2), and then subjecting the silyl group of R 5 to a desilylation reaction. It can be produced by substituting with a hydrogen atom.
  • the boron-containing conjugated polyene compound according to the present embodiment has a conjugated polyene skeleton and a boron-containing group bonded to the conjugated polyene skeleton. Therefore, according to the boron-containing conjugated polyene compound according to the present embodiment, the conjugated polyene skeleton can be easily introduced into the target compound by a reaction starting from the boron-containing group (for example, a cross-coupling reaction).
  • the boron-containing group is preferably a borono group or a derivative group thereof.
  • the boron-containing conjugated polyene compound according to the present embodiment can be applied to electronic materials and the like as a ⁇ -conjugated compound having a boron-containing group.
  • the boron-containing group is preferably a boryl group or a derivative group thereof.
  • the boron-containing conjugated polyene compound according to the present embodiment can have two or more boron-containing groups, and in this case, a polymer compound obtained by cross-coupling polymerization (for example, polymerization with a dihalogenated aromatic compound) It can be suitably used for the production of, for example.
  • the boron-containing group is preferably a borono group or a derivative group thereof.
  • the present invention is not limited to these.
  • one aspect of the present invention relates to a method for producing a conjugated polyene compound using the above-mentioned boron-containing conjugated polyene compound.
  • the method for producing a conjugated polyene includes a first step of obtaining a reaction solution containing a boron-containing conjugated polyene compound by the above-described method for producing a boron-containing conjugated polyene compound, and a coupling reaction catalyst And a third step of performing a coupling reaction by adding a third raw material compound having a reactive group capable of performing a coupling reaction with the boron-containing group.
  • the first step may be, for example, a step of producing the above-mentioned boron-containing conjugated polyene compound in a reaction system by reacting the first raw material compound and the second raw material compound in the presence of a metal catalyst.
  • the second step may be a step of adding a coupling reaction catalyst and a third raw material compound to the reaction system. According to such a one-pot reaction, a target conjugated polyene compound can be efficiently produced.
  • a continuous coupling reaction can be performed in one pot without recovering the boron-containing conjugated polyene compound from the reaction system after the reaction. This point can be said to be a great advantage of the above-described method for producing a boron-containing conjugated polyene compound.
  • the coupling reaction catalyst is not particularly limited, and can be appropriately selected and used from known coupling reaction catalysts.
  • Specific examples of the coupling reaction catalyst include, for example, known catalysts (eg, palladium catalyst, nickel catalyst, iron complex catalyst, etc.) used in the Suzuki-Miyaura coupling reaction such as [Pd (PPh 3 ) 4 ].
  • Examples include an immobilized catalyst (eg, an immobilized palladium catalyst, an immobilized nickel catalyst, an immobilized iron catalyst, etc.) and a metal fine particle catalyst (eg, a palladium fine particle catalyst, a nickel fine particle catalyst, an iron fine particle catalyst, etc.).
  • the reactive group of the third raw material compound is not particularly limited as long as it is a functional group capable of performing a coupling reaction with a boron-containing group.From the viewpoint of excellent substrate selectivity and reactivity, the reactive group is a halogeno group. Is preferred.
  • reaction conditions for the coupling reaction are not particularly limited, and can be appropriately selected from known reaction conditions for the coupling reaction.
  • Example 1-1 A boron-containing conjugated polyene compound (A-1) was synthesized by the following method.
  • Example 1-2 A boron-containing conjugated polyene compound (A-1) was synthesized by the following method.
  • Example 2 A boron-containing conjugated polyene compound was synthesized by the following method.
  • Example 3 A boron-containing conjugated polyene compound was synthesized by the following method.
  • Example 4 A boron-containing conjugated polyene compound was synthesized by the following method.
  • diphenylacetylene 32.09 mg, 0.180 mmol
  • 2- ⁇ (E) -1,3-butadienyl ⁇ -4,4,4 was dissolved therein.
  • 5,5-tetramethyl-1,3,2-dioxaborolane (36.0 ⁇ L, 0.180 mmol) was added, and then [Ru (naphthalene) (cod)] (6.07 mg, 0.0180 mmol) was further added. After 5 minutes at room temperature, the reaction was completed, and a boron-containing conjugated polyene compound (A-4) was obtained with a yield of 63%.
  • Example 5 A boron-containing conjugated polyene compound was synthesized by the following method.
  • Example 6 A boron-containing conjugated polyene compound was synthesized by the following method.
  • Example 7 A boron-containing conjugated polyene compound was synthesized by the following method.
  • Example 8 A boron-containing conjugated polyene compound was synthesized by the following method.
  • Example 9 A boron-containing conjugated polyene compound was synthesized by the following method.
  • Example 10 A boron-containing conjugated polyene compound was synthesized by the following method.
  • Example 11 A boron-containing conjugated polyene compound was synthesized by the following method.
  • Example 12 A boron-containing conjugated polyene compound was synthesized by the following method.
  • 1-pentynylboronic acid pinacol ester (51.0 ⁇ L, 0.222 mmol) and 2- ⁇ (E) -1,3-butadienyl ⁇ -4,4,5,5-tetramethyl-1,3 , 2-dioxaborolane (40.4 ⁇ L, 0.224 mmol) was dissolved in benzene-d 6 (0.6 mL), and [Ru (naphthalene) (cod)] (7.59 mg, 0.0225 mmol) was further added.
  • [Ru (naphthalene) (cod)] (7.59 mg, 0.0225 mmol) was further added.
  • boron-containing conjugated polyene compounds (A-108) and (A-109) were produced in a reaction time of 3 hours with a yield of 34% (production ratio 25/75).
  • Example 13 A boron-containing conjugated polyene compound was synthesized by the following method.
  • Example 14 A boron-containing conjugated polyene compound was synthesized by the following method.
  • Example 15 According to the following method, the synthesis of the boron-containing conjugated polyene compound and the subsequent cross-coupling reaction were performed in one pot to synthesize a conjugated polyene compound.
  • Example 16 According to the following method, the synthesis of the boron-containing conjugated polyene compound and the subsequent cross-coupling reaction were performed in one pot to synthesize a conjugated polyene compound.
  • Example 17 According to the following method, the synthesis of the boron-containing conjugated polyene compound and the subsequent cross-coupling reaction were performed in one pot to synthesize a conjugated polyene compound.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'un composé de polyène conjugué contenant du bore, le procédé comprenant une étape consistant à faire réagir un premier composé d'une matière première ayant une triple liaison carbone-carbone et un second composé d'une matière première ayant un groupe 1,3-butadiène-4,4-diyle et ayant un squelette di(ou poly)ène conjugué comprenant deux doubles liaisons carbone-carbone dans ledit groupe, la réaction étant effectuée en présence d'un catalyseur métallique, pour obtenir un composé polyène conjugué contenant du bore qui a un squelette polyène conjugué comprenant au moins trois doubles liaisons carbone-carbone, le procédé étant tel que le premier composé de matière première et/ou le second composé de matière première ont un groupe contenant du bore lié à un atome de carbone constituant une triple liaison ou un squelette di(ou poly)ène conjugué, et le composé polyène conjugué contenant du bore a un groupe contenant du bore lié à un atome de carbone constituant le squelette polyène conjugué.
PCT/JP2019/036830 2018-09-19 2019-09-19 Composé polyène conjugué contenant du bore, procédé de production associé et procédé de production d'un composé polyène conjugué Ceased WO2020059824A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010534240A (ja) * 2007-07-23 2010-11-04 ザ ボード オブ トラスティーズ オブ ザ ユニバーシティ オブ イリノイ ボロン酸の反応性の調節系

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* Cited by examiner, † Cited by third party
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Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010534240A (ja) * 2007-07-23 2010-11-04 ザ ボード オブ トラスティーズ オブ ザ ユニバーシティ オブ イリノイ ボロン酸の反応性の調節系

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
ARNDT, M. ET AL.: "Diels-Alder Reactions for the Construction of Cyclopropylarenes", EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2012, pages 3112 - 3121 *
AUVINET, A. ET AL.: "Ambient-Temperature Cobalt- Catalyzed Cycloaddition Strategies to Aromatic Boronic Esters", JOURNAL OF ORGANIC CHEMISTRY, vol. 75, 2010, pages 3893 - 3896, XP055017244, DOI: 10.1021/jo1004907 *
CORNIL, J. ET AL.: "Heck Coupling Using a Vinyliodo-MIDA Boronate: An Efficient and Modular Access to Polyene Frameworks", ORGANIC LETTERS, vol. 17, 2015, pages 948 - 951, XP055694764 *
DANZ, M. ET AL.: "Understanding the regioselectivity in Scholl reactions for the synthesis of oligoarenes", CHEMICAL COMMUNICATIONS, vol. 48, 2012, pages 377 - 379, XP055694752 *
GURSKII, M. E. ET AL.: "Electrocyclic ring opening on borylation of cyclooctatetraene dianion", METALLOORGANICESKAJA CHIMIJA, vol. 4, 1991, pages 202 - 203 *
HIRANO, M. ET AL.: "Catalytic cross-dimerisation giving reactive borylated polyenes toward cross- coupling", CHEMICAL COMMUNICATIONS, vol. 55, August 2019 (2019-08-01), pages 10527 - 10530, XP055694730 *
KIYOTA, S. ET AL.: "Ru(O)-Catalyzed Direct Coupling of Internal Alkynes with Conjugated Dienes: An Efficient Access to Conjugated Trienes", ORGANOMETALLICS, vol. 35, 2016, pages 4033 - 4043, XP055694825 *
KIYOTA, S. ET AL.: "Ru(O)-Catalyzed Straightforward Synthesis of Conjugated Tetraenes: An Approach using Two Internal Alkynes with 1, 3-Butadiene", ORGANOMETALLICS, vol. 37, January 2018 (2018-01-01), pages 227 - 234, XP055694823 *
KURAMOCHI, AYUMI ET AL.: "Catalytic synthesis of conjugated triene building block having reaction active boron substituent", LECTURE PREPRINTS OF THE 99TH SPRING 2019 ANNUAL MEETING OF CSJ, March 2019 (2019-03-01) *
LEBOEUF, D. ET AL.: "Cobalt-Mediated Linear 2: 1 Co-oligomerization of Alkynes with Enol Ethers to Give 1-Alkoxy-l, 3, 5-Trienes: A Missing Mode of Reactivity", CHEMISTRY A EUROPEAN JOURNAL, vol. 16, 2010, pages 8904 - 8913 *
WLODARCZYK, A. ET AL.: "Mixed-valence dinuclear molybdenum complexes with benzenediamido and dianilido bridges: comparison with related phenolato and dipyridyl species, and with their pentammineruthenium analogues", JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS, 1997, pages 3287 - 3298, XP055694821 *

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