CN113980044A - Preparation method of Ir-O-P type catalyst diboronic acid/ester compound - Google Patents

Preparation method of Ir-O-P type catalyst diboronic acid/ester compound Download PDF

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CN113980044A
CN113980044A CN202111464125.6A CN202111464125A CN113980044A CN 113980044 A CN113980044 A CN 113980044A CN 202111464125 A CN202111464125 A CN 202111464125A CN 113980044 A CN113980044 A CN 113980044A
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iridium
ester compound
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CN113980044B (en
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毛帅
袁博
张三奇
陈艺铭
赵亚浩
王欣宇
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Xian Jiaotong University
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
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    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract

The invention discloses a preparation method of an Ir-O-P type catalyst diboronic acid/ester compound, which belongs to the technical field of organic synthesis and comprises the following steps: under the air condition, the Ir metal complex and the phosphine ligand form an active Ir-O-P type catalyst; under the anhydrous and anaerobic condition, adding an organic boron source [ B ], a beta-N-aryl (alkyl) substrate and an Ir-O-P type catalyst into an organic solvent, reacting at 60-120 ℃, and after the reaction is finished, carrying out post-treatment to obtain the aryl (alkyl) diboronic acid/boric acid ester compound. The reaction can obtain the aryl (alkyl) diboronic acid/boric acid ester compound by a one-pot method, and overcomes the limitation that the compound needs to be synthesized in multiple steps and the substrate range is limited. In addition, in the preparation of the aryl triazene diboride, the target compound can be obtained with high yield even if no ligand is added, and based on the advantages, the method expands to gram-level reaction and also shows very high yield, thereby laying a good foundation for the application in the fields of drug synthesis or material development.

Description

Preparation method of Ir-O-P type catalyst diboronic acid/ester compound
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to research and development of a novel Ir-O-P type catalyst and application thereof in preparation of aryl (alkyl) diboronic acid/boric acid ester compounds.
Background
The activation of C-H bond catalyzed by metal is a new organic synthesis method which is developed rapidly at present. The formation of the C-B bond is one of the important forms of C-H bond activation. Due to the unique chemical properties of organoboron (borane, boric acid and boric acid ester), the functional group transformation of various forms can be realized, and the organoboron has important application value for modification of drug structures and development of new materials.
In the prior art, only aryl hydrazone diborides and diborides of 2-phenylpyridine derivatives can be synthesized due to the limitation of raw materials and methods.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an Ir-O-P type catalyst diboronic acid/ester compound, which has the advantages of simple operation, cheap and easily obtained raw materials, avoidance of the use of expensive organic ligands, and convenience for large-scale preparation and application, and in addition, aryl oximes, aryl hydrazones, aryl triazenes and 2-phenylpyridine derivatives have very mature and simple synthesis methods. However, the conventional method can synthesize only the arylhydrazone diboride and the diboride of the 2-phenylpyridine derivative, which are limited by the raw materials and the method. However, by using the method, various aryl (alkyl) diboronic acid/boric acid ester compounds can be obtained by a one-pot method only by using cheap and easily available triphenylphosphine as a ligand. More significantly, in the preparation of aryltriazene diborides, the target compounds can be obtained in higher yields even without the addition of ligands. Based on the above advantages, the method also shows very high yield when expanding to gram-scale reaction, lays a good foundation for the application in the field of drug synthesis or material development, and solves the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of an Ir-O-P type catalyst diboronic acid/ester compound comprises the following steps:
s1, under the air condition, forming Ir-O-P type active catalyst through the reaction of metal iridium species and ligand in organic solvent, then adding beta-N aryl (alkyl) substrate and organic boron source [ B ] under the anaerobic condition, and obtaining aryl (alkyl) diboronic acid/boric acid ester compound; under the anhydrous and oxygen-free conditions, oxidizing and adding a metal iridium catalyst and a beta-N aryl (alkyl) substrate in an organic solvent and an organic boron source [ B ] to obtain an aryl (alkyl) diboronic acid/boric acid ester compound;
s2, carrying out oxidation addition on an Ir-O-P type active catalyst and a beta-N-aryl (alkyl) substrate to activate a carbon-hydrogen bond, and carrying out boron transfer and reduction elimination processes to form an aryl (alkyl) diboronic acid/boric acid ester compound; the metal iridium catalyst and an organic boron source are subjected to oxidation addition, and then are subjected to oxidation addition, boron transfer and reduction elimination with an aryltriazene substrate to form an ortho-substituted aryltriazene diboronic acid/boric acid ester compound;
s3, post-processing the formed aryl (alkyl) diboronic acid/boric acid ester compound.
Further optimizing the technical scheme, the reaction temperature of the steps S1-S2 is 60-120 ℃, and the reaction time is 12-120 hours;
the organic boron source [ B ] comprises pinacol diborate, neopentyl glycol diborate, bis-catechol borate, tetramethyl diboron, tetra (dimethylamino) diboron and 1-pinacol-2- (1,8) naphthalene diamine diborate;
the beta-N aryl (alkyl) substrate comprises beta-N aryl (alkyl) compounds including aryl oximes, aryl hydrazones, aryl triazenes and 2-phenylpyridine derivatives;
the metal iridium catalyst comprises methoxycyclooctadiene iridium, cyclooctadiene iridium chloride, iridium acetate, iridium dioxide, iridium chloride, dodecacarbonyltetrairidium, tris (acetylacetone) iridium, 1, 5-cyclooctadiene (. eta.5-indene) iridium, tris [ 2-phenylpyridine-C2, N ] iridium, carbonylbis (triphenylphosphine) iridium chloride, bis (1, 5-cyclooctadiene) iridium tetrafluoroborate, bis (4, 6-difluorophenylpyridine-N, C2) iridium picolinate;
the phosphine-containing ligand comprises aryl phosphine and alkyl phosphine ligands including triphenylphosphine, tri (p-methylphenyl) phosphine, tributylphosphine, 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl, benzyldiphenyl phosphine, tri (2-tolyl) phosphine, bis [ (2-diphenylphosphino) phenyl ] ether, 2' -bis (diphenylphosphino) biphenyl;
the organic solvent comprises tetrahydrofuran, toluene, p-xylene, cyclohexane dichloromethane, chloroform, ethyl acetate, acetonitrile, benzene or a mixed solvent of the above, and the organic solvent can fully dissolve the raw materials participating in the reaction and can be a protic solvent, an aprotic solvent or a mixed solvent of the protic solvent and the aprotic solvent;
further, the structure of the organic boron source [ B ] is shown in formulas (I) to (VI):
Figure BDA0003390595850000031
further, the structure of the beta-N-aryl (alkyl) substrate is shown in formulas (VII) to (XV):
Figure BDA0003390595850000032
further, the structure of the ar (alk) yl diboronic acid/borate compound is shown as formulas (XVI) to (XXIV):
Figure BDA0003390595850000041
further, in the formulae (VII) to (XXIV), R1The method comprises the following steps: halogen substituted at any position, such as F, Cl, Br, I, alkyl and substituted alkyl, such as methyl, trifluoromethyl, methoxy, aryl, such as phenyl, heteroaryl, such as pyridine, as partial substituents shown below;
H，
Figure BDA0003390595850000042
R2the method comprises the following steps: substitution at any positionHalogen such as F, Cl, Br, I, hydrogen atoms, alkyl groups and substituted alkyl groups such as methyl, isopropyl, isobutyl, benzyl, saturated chain or cyclic alkyl groups, partial substituents as shown below:
H，
Figure BDA0003390595850000043
Figure BDA0003390595850000044
R3including alkyl and substituted alkyl, e.g. methyl, R2And R3Ring-forming type, such as piperidine ring, morpholine ring, piperazine ring.
Further optimizing the technical scheme, the preparation method of the active catalyst also comprises the following other methods:
1) the iridium simple substance is reacted with acid to form salt, and then the salt is reacted with triaryl/alkyl phosphine in an organic solvent under the air condition to generate the iridium-containing iridium simple substance, and the acid is sulfuric acid, hydrochloric acid, hydrofluoric acid or acetic acid.
2) The iridium-containing salt or complex and triaryl/alkyl phosphine are reacted in an organic solvent under the air condition to generate the iridium-containing complex.
Further, the active catalyst formed by the reaction with the representative triphenylphosphine has the formula C54H43IrOP3The structural feature is that the material contains Ir-O-P bond, and the structure is as follows:
Figure BDA0003390595850000051
further optimizing the technical scheme, the feeding ratio of the beta-N-aryl (alkyl) substrate to the organic boron source [ B ] is 1.0: 1.0-4.0 percent, the addition of the catalyst and the ligand is 0.005-10 percent of the substrate, and the full reaction is carried out under the optimized condition, so as to reduce the dosage of reactants and improve the atom economy.
In order to further optimize the technical scheme, the aryl (alkyl) diboronic acid/boric acid ester compound is one of compounds shown in formulas (I-1) to (I-37), and the formulas (I-1) to (I-37) are shown as follows:
Figure BDA0003390595850000061
Figure BDA0003390595850000071
further optimizing the technical scheme, the reaction formula of the beta-N-aryl (alkyl) substrate and the organic boron source [ B ] is as follows:
Figure BDA0003390595850000072
further optimizing the technical solution, in S3, the post-processing includes: concentrating, mixing with silica gel, purifying by column chromatography, and recrystallizing or pulping part of the product.
Compared with the prior art, the invention provides a preparation method of an Ir-O-P type catalyst diboronic acid/ester compound, which has the following beneficial effects:
1. according to the preparation method of the Ir-O-P type catalyst diboronic acid/ester compound, the aryl (alkyl) diboronic acid/borate compound is obtained by a one-pot method, the limitation that the compound needs to be synthesized in multiple steps and the substrate range is limited is overcome, the target compound can be obtained at a high yield in the preparation of the aryl triazene diboride even if a ligand is not added, and based on the advantages, the method expands to gram-level reaction and also shows a very high yield, so that a good foundation is laid for the application in the field of medicine synthesis or material development.
2. The preparation method of the Ir-O-P type catalyst diboronic acid/ester compound is convenient to operate, simple in post-treatment, cheap and easily available in reaction raw materials, strong in designability of reaction substrates, good in compatibility of substrate functional groups, capable of designing and synthesizing the required aryl (alkyl) diboronic acid/borate compound according to actual needs, and strong in practicability.
Drawings
FIG. 1 is a schematic structural diagram of various ar (alk) yl diboronic acid/boronic ester compounds (I-1) to (I-22) prepared by the preparation method provided by the invention;
FIG. 2 is a schematic structural diagram of a plurality of ar (alk) yl diboronic acid/borate compounds (I-23) - (I-37) prepared by the preparation method provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
a preparation method of an Ir-O-P type catalyst diboronic acid/ester compound comprises the following steps: under the anhydrous and oxygen-free conditions, adding an organic boron source [ B ], a beta-N-aryl (alkyl) substrate, a metal iridium catalyst and an organic phosphine ligand into an organic solvent, reacting at 60-120 ℃, and after the reaction is finished, carrying out post-treatment to obtain the aryl (alkyl) diboronic acid/boric acid ester compound.
The structure of the organic boron source [ B ] is shown in formulas (I) to (IV):
Figure BDA0003390595850000091
the structure of the beta-N-aryl (alkyl) substrate is shown in formulas (IV) to (VII):
Figure BDA0003390595850000092
the structure of the aryl (alkyl) diboronic acid/boric acid ester compound is shown as the following formula:
Figure BDA0003390595850000093
the mol ratio of the beta-N-aryl (alkyl) substrate to the organic boron source [ B ] is 1.0: 1.0 to 4.0.
The reaction formula is as follows:
Figure BDA0003390595850000101
through the research of the reaction mechanism, the oxidative addition and reductive elimination process is proved through control experiments. The active catalyst is generated by the coordination of metallic iridium and beta-N aryl (alkyl) substrate or phosphine-containing ligand and the oxidative addition of the metallic iridium and an organic boron source; the active catalyst and beta-N-aryl (alkyl) substrate are oxidized and added to activate carbon-hydrogen bond, and then aryl (alkyl) diboronic acid/boric acid ester compound is formed through boron transfer and reduction elimination processes.
In the present invention, the optional post-processing procedure includes: concentrating, mixing with silica gel, purifying by column chromatography, and recrystallizing or pulping part of the product.
Preferably, R1Can be fluorine, chlorine, bromine, iodine, methyl, methoxy, trifluoromethyl and phenyl at any position, in which case the beta-N aryl (alkyl) substrate is easily obtained and the reaction yield is high.
Preferably, R2May be a hydrogen atom or a methyl group, or may be bonded to R3Forming pyridine ring or pyrazole ring, and the beta-N aryl (alkyl) substrate is easy to obtain and has high reaction yield.
Preferably, R3Can be diisopropylamino, methoxy, or with R2Forming pyridine ring or pyrazole ring, and the beta-N aryl (alkyl) substrate is easy to obtain and has high reaction yield.
Preferably, the reaction time is 12-120 hours, the reaction completeness is difficult to ensure due to too short reaction time, and the reaction cost is increased due to too long reaction time.
In the present invention, the organic solvent capable of sufficiently dissolving the raw material allows the reaction to occur, but the difference in reaction efficiency is large, and an aprotic solvent is preferable because the interaction with the imine structural unit of the reaction substrate can be avoided and the reaction can be performed normally.
Preferably, the organic solvent is tetrahydrofuran, N-hexane, N, N-dimethylformamide, N, N-dimethyl sulfoxide; more preferably, when the organic solvent is tetrahydrofuran, the conversion rate of each raw material in the reaction is high and the post-treatment is simple. The dosage of the organic solvent can completely dissolve the raw material, and the dosage of the organic solvent used by 1mmol of beta-N-aryl (alkyl) substrate is 1-2 mL.
The triphenylphosphine is the most preferred ligand because of the higher yield and cheapest availability of triphenylphosphine. Other triaryl (alkyl) phosphines may also be used as ligands to allow the reaction, such as triphenylphosphine, tris (p-methylphenyl) phosphine, tricyclohexylphosphine, and the like.
Preferably, the metal iridium catalyst is methoxy cyclooctadiene iridium, and the reaction yield is highest. Other iridium catalysts may also be used to effect the reaction, such as cyclooctadiene iridium chloride.
As a further preferred, as shown in FIGS. 1 and 2, the ar (alk) yl diboronic acid/boronic acid ester compound is one of the compounds represented by the formulae (I-1) to (I-37).
In the above preparation method, the organic boron source [ B ], the metal iridium catalyst and the triaryl (alkyl) phosphine are all commercially available products and can be purchased directly from the market, and the beta-N-aryl (alkyl) substrate can be purchased directly or prepared by a simple and convenient method.
Example two:
adding methoxycyclooctadiene iridium, triphenylphosphine, beta-N-aryl (alkyl) substrate, bis (pinacolato) borate and 2mL of organic solvent into a Schlenk tube with the raw material ratio of 10mL in the table 1, heating and stirring for reaction at 60-120 ℃, after the reaction is finished according to the reaction conditions in the table 2, concentrating, stirring with silica gel, and purifying by column chromatography to obtain the corresponding aryl (alkyl) diboronic acid/borate compound, wherein the reaction process is shown as the following formula:
Figure BDA0003390595850000111
TABLE 1
Figure BDA0003390595850000112
Figure BDA0003390595850000121
Figure BDA0003390595850000131
TABLE 2 reaction conditions and products obtained for the above examples
Figure BDA0003390595850000132
Figure BDA0003390595850000141
Figure BDA0003390595850000151
In Table 2, T is the reaction temperature and T is the reaction time.
Structural confirmation data of partial compound
Nuclear magnetic resonance of the ar (alk) yl diboronic acid/boronic acid ester compound (I-1) prepared from example I1: (1H NMR and13c NMR) the data were:
Figure BDA0003390595850000152
1H NMR(400MHz,Chloroform-d)δ7.83(d,J＝7.3Hz,2H),7.13(t,J＝7.4Hz,1H),5.16–5.08(m,1H),3.97-3.93(m,1H),1.32(d,J＝6.8Hz,12H),1.25(s,24H)；13C NMR(101MHz,Chloroform-d)δ165.2,138.7,123.6,83.1,48.1,45.3,25.0,23.9,19.8.IR(ν,cm-1):2976,1580,1460,1392,1369,1331,1310,1300,1256,1221,1148,1132,966,881,847,775,652.
nuclear magnetic resonance of ar (alk) yl diboronic acid/boronic acid ester compound (I-2) prepared from example I2: (1H NMR and13c NMR) detection data of
Figure BDA0003390595850000153
1H NMR(400MHz,Chloroform-d)δ7.89(s,2H),1.36(s,6H),1.31(s,12H),1.26(s,6H),1.24(s,12H)；13C NMR(101MHz,Chloroform-d)δ163.9,133.7(d,J＝3.6Hz),117.6,83.6,24.9,24.5.IR(ν,cm-1):2978,2926,1468,1368,1271,1140,1103,1067,850,720.
Nuclear magnetic resonance of ar (alk) yl diboronic acid/boronic acid ester compound (I-3) prepared from example I3 (II)1H NMR and13c NMR) detection data of
Figure BDA0003390595850000161
1H NMR(400MHz,Chloroform-d)δ7.90(s,2H),5.14–5.03(m,1H),4.01–3.90(m,1H),1.31(d,J＝6.7Hz,18H),1.24(s,18H)；13C NMR(101MHz,Chloroform-d)δ163.9,140.7,117.6,83.3,48.3,45.6,24.9,23.7,19.6.IR(ν,cm-1):2978,1468,1371,1337,1313,1271,1140,1103,1067,964,849,603.
Nuclear magnetic resonance of ar (alk) yl diboronic acid/boronic acid ester compound (I-23) prepared from example I23: (1H NMR and13c NMR) detection data of
Figure BDA0003390595850000162
1H NMR(400MHz,Chloroform-d)δ8.79(d,J＝8.2Hz,1H),8.66(d,J＝5.6Hz,1H),7.92(t,J＝7.8Hz,1H),7.78(d,J＝7.3Hz,2H),7.35(q,J＝7.5Hz,2H),1.40(s,24H)；13C NMR(101MHz,Chloroform-d)δ157.8,142.7,141.8,141.7,135.0,130.0,122.5,121.7,82.1,26.2.
Nuclear magnetic resonance of the ar (alk) yl diboronic/boronic acid ester compound (I-35) prepared from example I35: (1H NMR and13c NMR) detection data of
Figure BDA0003390595850000163
1H NMR(400MHz,Chloroform-d)δ8.93(d,J＝2.5Hz,1H),7.80(d,J＝2.2Hz,1H),7.77(d,J＝7.3Hz,2H),7.26(d,J＝14.6Hz,1H),6.46(t,J＝2.5Hz,1H),1.34(s,24H)；13C NMR(101MHz,Chloroform-d)δ145.8,136.4,135.1,129.6,126.8,108.4,82.7,25.3.
Example three:
the invention also discloses a novel water-resistant and oxygen-resistant Ir-O-P bond-containing metal iridium catalyst when preparing aryl (alkyl) diboronic acid/borate compounds, which can be widely used for a plurality of C-H bond boronization, has good substrate tolerance and better catalytic activity than various commercially available metal iridium catalysts.
The invention has the beneficial effects that:
1. according to the preparation method of the Ir-O-P type catalyst diboronic acid/ester compound, the aryl (alkyl) diboronic acid/borate compound is obtained by a one-pot method, the limitation that the compound needs to be synthesized in multiple steps and the substrate range is limited is overcome, the target compound can be obtained at a high yield in the preparation of the aryl triazene diboride even if a ligand is not added, and based on the advantages, the method expands to gram-level reaction and also shows a very high yield, so that a good foundation is laid for the application in the field of medicine synthesis or material development.
2. The preparation method of the Ir-O-P type catalyst diboronic acid/ester compound is convenient to operate, simple in post-treatment, cheap and easily available in reaction raw materials, strong in designability of reaction substrates, good in compatibility of substrate functional groups, capable of designing and synthesizing the required aryl (alkyl) diboronic acid/borate compound according to actual needs, and strong in practicability.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (7)

1. A preparation method of an Ir-O-P type catalyst diboronic acid/ester compound is characterized by comprising the following steps:
s1, under the air condition, forming Ir-O-P type active catalyst through the reaction of metal iridium species and ligand in organic solvent, then adding beta-N aryl (alkyl) substrate and organic boron source [ B ] under the anaerobic condition, and obtaining aryl (alkyl) diboronic acid/boric acid ester compound; under the anhydrous and oxygen-free conditions, oxidizing and adding a metal iridium catalyst and a beta-N aryl (alkyl) substrate in an organic solvent and an organic boron source [ B ] to obtain an aryl (alkyl) diboronic acid/boric acid ester compound;
s2, carrying out oxidation addition on an Ir-O-P type active catalyst and a beta-N-aryl (alkyl) substrate to activate a carbon-hydrogen bond, and carrying out boron transfer and reduction elimination processes to form an aryl (alkyl) diboronic acid/boric acid ester compound; the metal iridium catalyst and an organic boron source are subjected to oxidation addition, and then are subjected to oxidation addition, boron transfer and reduction elimination with an aryltriazene substrate to form an ortho-substituted aryltriazene diboronic acid/boric acid ester compound;
s3, post-processing the formed aryl (alkyl) diboronic acid/boric acid ester compound.
2. The method for preparing the diboronic acid/ester compound as the Ir-O-P type catalyst according to claim 1, wherein the method comprises the following steps:
the reaction temperature of the steps S1-S2 is 60-120 ℃, and the reaction time is 12-120 hours;
the organic boron source [ B ] comprises pinacol diborate, neopentyl glycol diborate, bis-catechol borate, tetramethyl diboron, tetra (dimethylamino) diboron and 1-pinacol-2- (1,8) naphthalene diamine diborate;
the beta-N aryl (alkyl) substrate comprises beta-N aryl (alkyl) compounds including aryl oximes, aryl hydrazones, aryl triazenes and 2-phenylpyridine derivatives;
the metal iridium species include methoxycyclooctadiene iridium, cyclooctadiene iridium chloride, iridium acetate, iridium dioxide, iridium chloride, dodecacarbonyltetrairidium, tris (acetylacetonato) iridium, 1, 5-cyclooctadiene (. eta.5-indene) iridium, tris [ 2-phenylpyridine-C2, N ] iridium, carbonylbis (triphenylphosphine) iridium chloride, bis (1, 5-cyclooctadiene) iridium tetrafluoroborate, bis (4, 6-difluorophenylpyridine-N, C2) iridium picolinate;
the phosphine-containing ligand comprises aryl phosphine and alkyl phosphine ligands including triphenylphosphine, tri (p-methylphenyl) phosphine, tributylphosphine, 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl, benzyldiphenyl phosphine, tri (2-tolyl) phosphine, bis [ (2-diphenylphosphino) phenyl ] ether, 2' -bis (diphenylphosphino) biphenyl;
the organic solvent comprises tetrahydrofuran, toluene, p-xylene, cyclohexane dichloromethane, chloroform, ethyl acetate, acetonitrile, benzene or a mixed solvent of the above, and the organic solvent can fully dissolve the raw materials participating in the reaction and can be a protic solvent, an aprotic solvent or a mixed solvent of the protic solvent and the aprotic solvent;
further, the structure of the organic boron source [ B ] is shown in formulas (I) to (VI):
Figure FDA0003390595840000021
further, the structure of the beta-N-aryl (alkyl) substrate is shown in formulas (VII) to (XV):
Figure FDA0003390595840000022
further, the structure of the ar (alk) yl diboronic acid/borate compound is shown as formulas (XVI) to (XXIV):
Figure FDA0003390595840000031
further, in the formulae (VII) to (XXIV), R1The method comprises the following steps: halogen substituted at any position, such as F, Cl, Br, I, alkyl and substituted alkyl, such as methyl, trifluoromethyl, methoxy, aryl, such as phenyl, heteroaryl, such as pyridine, as partial substituents shown below;
H，
Figure FDA0003390595840000032
R2the method comprises the following steps: halogen substituted at any position, such as F, Cl, Br, I, hydrogen atom, alkyl and substituted alkyl, such as methyl, isopropyl, isobutyl, benzyl, saturated chain or cyclic alkyl, partial substituents as shown below:
H，
Figure FDA0003390595840000033
Figure FDA0003390595840000034
R3including alkyl and substituted alkyl, e.g. methyl, R2And R3In the ring-forming type, e.g. piperidine ring, morpholineA ring, a piperazine ring.
3. The method for preparing diboronic acid/ester compound as an Ir-O-P type catalyst according to claim 1, wherein the Ir-O-P type active catalyst is prepared by the following methods:
1) the iridium simple substance is reacted with acid to form salt, and then the salt is reacted with phosphine ligand in an organic solvent under the air condition to generate the iridium-containing iridium complex salt, wherein the iridium simple substance is iridium powder, and the acid is sulfuric acid, hydrochloric acid, hydrofluoric acid or acetic acid.
2) The iridium-containing salt or complex and triaryl/alkyl phosphine are reacted in an organic solvent under the air condition to generate the iridium-containing complex.
Further, the active catalyst formed by the reaction with the representative triphenylphosphine has a molecular formula of C54H43IrOP3The structural feature is that the material contains Ir-O-P bond, and the structure is as follows:
Figure FDA0003390595840000041
4. the method for preparing the diboronic acid/ester compound as the Ir-O-P type catalyst according to claim 1, wherein the dosage ratio of the beta-N-ar (alk) yl substrate to the organic boron source [ B ] is 1.0: 1.0-4.0 percent, the addition of the catalyst and the ligand is 0.005-10 percent of the substrate, and the full reaction is carried out under the optimized condition, so as to reduce the dosage of reactants and improve the atom economy.
5. The method for preparing diboronic acid/ester compound as an Ir-O-P type catalyst according to claim 1, wherein the ar (alk) yl diboronic acid/boronate compound is one of compounds represented by formulas (I-1) to (I-37), and the formulas (I-1) to (I-37) are as follows:
Figure FDA0003390595840000051
Figure FDA0003390595840000061
6. the method for preparing diboronic acid/ester compound as an Ir-O-P type catalyst according to claim 4, wherein the reaction formula of the β -N-ar (alk) substrate and the organic boron source [ B ] is as follows:
Figure FDA0003390595840000062
7. the method for preparing the diboronic acid/ester compound as the Ir-O-P type catalyst according to claim 1, wherein in the step S3, the post-treatment process comprises the following steps: concentrating, mixing with silica gel, purifying by column chromatography, and recrystallizing or pulping part of the product.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030109713A1 (en) * 2001-07-13 2003-06-12 Board Of Trustees Operating Michigan State University Process for the catalytic synthesis of biaryls and polymers from aryl compounds
US20050148775A1 (en) * 2002-03-06 2005-07-07 Norio Miyaura Process for production of heteroaryl-type boron compounds with iridium catalyst
US20100041834A1 (en) * 2007-04-02 2010-02-18 The Board of Regents of the Nevada System of Higher Education on Behalf of the UNLV Incorporation of functional groups into polymers using C-H activation
JP2015054823A (en) * 2013-09-10 2015-03-23 住友化学株式会社 Method for manufacturing boron compound
CN112724168A (en) * 2020-12-29 2021-04-30 西安交通大学 Chiral pyridine derived N, B ligand, preparation method and application in iridium-catalyzed asymmetric boronation reaction

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030109713A1 (en) * 2001-07-13 2003-06-12 Board Of Trustees Operating Michigan State University Process for the catalytic synthesis of biaryls and polymers from aryl compounds
US20050148775A1 (en) * 2002-03-06 2005-07-07 Norio Miyaura Process for production of heteroaryl-type boron compounds with iridium catalyst
US20100041834A1 (en) * 2007-04-02 2010-02-18 The Board of Regents of the Nevada System of Higher Education on Behalf of the UNLV Incorporation of functional groups into polymers using C-H activation
JP2015054823A (en) * 2013-09-10 2015-03-23 住友化学株式会社 Method for manufacturing boron compound
CN112724168A (en) * 2020-12-29 2021-04-30 西安交通大学 Chiral pyridine derived N, B ligand, preparation method and application in iridium-catalyzed asymmetric boronation reaction

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SHUAI MAO ET AL.: "Triazene as the Directing Group Achieving Highly Ortho-Selective Diborylation and Sequential Functionalization", 《ORGANIC LETTERS》 *
徐志安等: "铱催化芳基C-H键硼化反应合成硼酸酯聚三氟苯乙", 《广东化工》 *
邹晓亮等: "铱催化的（杂）芳烃远端区域选择性C—H硼化反应的最新进展", 《有机化学》 *

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