WO2024103458A1 - 一种具有质子响应功能的配体、金属铱络合物及其制备方法和应用 - Google Patents

一种具有质子响应功能的配体、金属铱络合物及其制备方法和应用 Download PDF

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WO2024103458A1
WO2024103458A1 PCT/CN2022/137414 CN2022137414W WO2024103458A1 WO 2024103458 A1 WO2024103458 A1 WO 2024103458A1 CN 2022137414 W CN2022137414 W CN 2022137414W WO 2024103458 A1 WO2024103458 A1 WO 2024103458A1
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formula
reaction
response function
ligand
iridium complex
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殷勤
荣念新
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Shenzhen Institute of Advanced Technology of CAS
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
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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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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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
    • B01J31/22—Organic complexes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups 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
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/58—Pyridine rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • 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
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium

Definitions

  • the present invention belongs to the metal organic field, and specifically relates to a ligand with proton response function, a metal iridium complex, and a preparation method and application thereof, and in particular relates to a ligand with proton response function, a cyclopentadienyl metal iridium complex, and a preparation method and application thereof.
  • Proton ligands can reversibly interconvert between two different electronic states by gaining or losing a proton.
  • the ligand controls the proton transfer of the proton response unit and the transfer of the hydride of the metal center from a suitable donor to an acceptor. Because of this feature, catalysts containing such ligands are often effectively used in hydride and proton response reactions such as dehydrogenation or hydrogen borrowing.
  • the properties (acid-base properties) and coordination mode of the proton response unit are key factors in achieving metal-ligand synergy.
  • metal iridium catalysts have excellent catalytic performance in related hydrogen transfer, such as the metal iridium catalysts shown in the following formulas 1 and 2:
  • Complex 1 was first reported by Yamaguchi in 2012. This type of complex exhibits excellent catalytic performance in the dehydrogenation reaction of aromatic alcohols through proton response.
  • the complex is obtained by complexing the ligand with metal iridium, and then reacting to obtain a dearomatized metal complex. During the reaction, the aromatization in the ligand is reconstructed by reacting with the substrate hydroxyl group, and then dehydrogenation is performed for dearomatization to complete the catalytic cycle. (Angew. Chem. Int. Ed. 2012, 51, 12790). This route first synthesizes the metal precursor 1-2, then complexes with the dinitrogen ligand to obtain the intermediate 1-4, and obtains compound 1 under the action of a strong base.
  • the ligands of the above two complexes have certain limitations in preparation, such as the difficulty in achieving divergent synthesis of ligands and the relative difficulty in derivatizing ligands, which results in relatively single types of catalysts and difficulty in establishing a catalyst library.
  • the object of the present invention is to provide a ligand with proton response function, a metal iridium complex, and a preparation method and application thereof.
  • the routes and methods for synthesizing complexes with such properties reported in the literature are relatively complicated, requiring the preparation of dearomatized metal complexes in advance, and realizing reconstructed aromatization in the reaction to achieve the function of proton response, and the synthesis methods of related ligands are relatively complicated.
  • the present invention aims to develop a new ligand and its iridium metal complex, which can simply and quickly prepare an iridium metal complex with proton response function from simple and readily available raw materials.
  • the complex can be dearomatized and re-aromatized in situ during the reaction, thereby avoiding the pre-preparation of dearomatized type ligands, achieving the purpose of reducing the synthesis steps and improving the ease of operation.
  • the synthesis of such ligands is simple and modularly synthesized, which is conducive to the establishment of ligand and complex libraries.
  • the present invention adopts the following technical solutions:
  • the present invention provides a ligand having a proton response function, wherein the ligand having a proton response function has a structure shown in the following formula L:
  • R 1 , R 2 , R 3 , and R 4 are each independently selected from any one of hydrogen, halogen, C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) linear or branched alkyl, C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) alkoxy, halogen-substituted C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) alkyl, or -NR a R b ;
  • R5 is selected from any one of substituted or unsubstituted C6-C12 (for example, C6, C7, C8, C9, C10, C11, C12, etc.) aryl, C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) linear or branched alkyl;
  • C6-C12 for example, C6, C7, C8, C9, C10, C11, C12, etc.
  • C1-C10 for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.
  • Ra and Rb are each independently selected from C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) linear or branched alkyl groups.
  • the substituent of the C6-C12 aryl group is selected from any one of halogen, C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) linear or branched alkyl, C1-C10 alkoxy (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.), halogen-substituted C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) alkyl or -NR c R d , or a combination of at least two thereof; R c and R d are each independently selected from C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) linear or branched alkyl (the C6-C12 aryl group may be monosubstituted or poly
  • R 1 , R 2 , R 3 and R 4 are each independently selected from any one of hydrogen, fluorine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-pentyl, n-hexyl, methoxy, ethoxy, trifluoromethyl or -N(Me) 2 .
  • the R 5 is selected from any one of unsubstituted or Re substituted phenyl, C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) straight chain or branched alkyl
  • the Re is selected from any one of hydrogen, fluorine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-pentyl, n-hexyl, methoxy, ethoxy, trifluoromethyl or -N(Me) 2 , or a combination of at least two of them (phenyl may be monosubstituted or polysubstituted).
  • the ligand having a proton response function has a structure as shown in the following formulas L-1 to L-10:
  • the present invention provides a method for preparing a ligand having a proton response function according to the first aspect, the preparation method comprising the following steps:
  • R 1 , R 2 , R 3 , R 4 and R 5 is consistent with that of the first aspect, and X is selected from any one of Cl, Br or I.
  • the molar ratio of the compound represented by formula I to the compound represented by formula II is (1-2):1 (wherein, "1-2" can be 1, 1.2, 1.4, 1.6, 1.8, 2, etc.).
  • the coupling reaction is carried out in the presence of a catalyst, and the catalyst comprises palladium acetate and/or tetrakis(triphenylphosphine)palladium.
  • the molar ratio of the compound represented by formula I to the catalyst is (30-45):1 (wherein, "30-45” can be 30, 33, 36, 39, 41, 43, 45, etc.).
  • step (1) the coupling reaction is carried out in degassed water.
  • the coupling reaction temperature is 90-110°C (for example, 90°C, 100°C, 110°C, etc.), and the reaction time is 4-6h (for example, 4h, 4.5h, 5h, 5.5h, 6h, etc.).
  • step (2) the molar ratio of the compound represented by formula III to the compound represented by formula IV is 1:(1-1.2) (wherein, "1-1.2” can be 1, 1.05, 1.1, 1.15, 1.2, etc.).
  • the condensation reaction is carried out in the presence of a base, and the base comprises any one of triethylamine, N,N-diisopropylethylamine or pyridine, or a combination of at least two thereof.
  • the molar ratio of the compound represented by formula III to the base is 1:(1.8-2.2) (wherein, "1.8-2.2” can be 1.8, 1.9, 2, 2.1, 2.2, etc.).
  • step (2) the condensation reaction is carried out in an organic solvent, and the organic solvent comprises any one of dichloroalkane, chloroform or toluene, or a combination of at least two thereof.
  • the condensation reaction temperature is 0-30°C (for example, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, etc.), and the reaction time is 8-15h (for example, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, etc.).
  • the present invention provides a metal iridium complex having a proton response function, wherein the ligand of the metal iridium complex having a proton response function is selected from the ligand having a proton response function according to the first aspect, and the metal iridium complex having a proton response function has a structure shown in the following formula Cp*Ir:
  • R 1 , R 2 , R 3 , R 4 and R 5 are consistent with those in the first aspect.
  • the metal iridium complex having a proton response function has a structure shown in the following formulas Cp*Ir-1 to Cp*Ir-10:
  • the present invention provides a method for preparing the metal iridium complex having a proton response function according to the third aspect, the preparation method comprising the following steps: complexing the compound represented by formula L with [Cp*IrCl 2 ] 2 to generate a metal iridium complex represented by formula Cp*Ir, the reaction formula being as follows:
  • R 1 , R 2 , R 3 , R 4 and R 5 are consistent with those in the first aspect.
  • the molar ratio of the compound represented by formula L to [Cp*IrCl 2 ] 2 is 1:(0.2-0.5) (wherein, "0.2-0.5” can be 0.2, 0.3, 0.4, 0.5, etc.).
  • the complexing reaction is carried out in the presence of a base, and the base includes any one or a combination of at least two of sodium acetate, sodium carbonate, potassium acetate or potassium carbonate, preferably sodium acetate.
  • the molar ratio of the compound represented by formula L to the base is 1:(2-5) (wherein "2-5" can be 2, 3, 4, 5, etc.).
  • the complexation reaction is carried out in an organic solvent, and the organic solvent includes any one of dichloromethane, toluene or tetrahydrofuran or a combination of at least two thereof, preferably dichloromethane.
  • the temperature of the complexation reaction is 20-30°C (for example, it can be 20°C, 22°C, 24°C, 26°C, 28°C, 30°C, etc.), and the time is 20-30h (for example, it can be 20h, 22h, 24h, 26h, 28h, 30h, etc.).
  • the present invention uses commercially available boric acid, pyridine amine compounds and metal iridium precursors to obtain a cyclopentadienyl iridium complex through a three-step reaction.
  • the catalytic performance of the cyclopentadienyl iridium complex in alcohol dehydrogenation is explored and studied.
  • a preparation method of a metal iridium complex with a proton response function is provided, which has the advantages of high yield, low cost, mild conditions, simple process and the like.
  • the present invention starts from simple and readily available raw materials and can prepare Cp*Ir metal complexes with proton response function in three steps. Compared with the best existing technologies reported in relevant literature, the present invention has obvious advantages such as economical starting raw materials, fewer reaction steps, relatively simple operation, and high overall yield.
  • the synthetic route does not involve highly toxic chemicals and is relatively environmentally friendly and green. More importantly, this method can be used to modularly synthesize diverse ligands, which is conducive to the establishment of ligand and complex libraries, thereby improving its broad spectrum in organic synthesis.
  • the present invention provides a use of the ligand with proton response function according to the first aspect or the metal iridium complex with proton response function according to the third aspect in catalytic hydrogen transfer reaction.
  • the hydrogen transfer reaction comprises an alcohol hydrogen transfer reaction.
  • the alcohol hydrogen transfer reaction includes an alpha alkylation reaction of acetophenone with benzyl alcohol or an alkylation reaction of aromatic hydrocarbons with benzyl alcohol.
  • the metal iridium complex provided by the present invention has high catalytic performance in catalyzing the alkylation reaction of ketones or olefins.
  • the ligand and the metal part of the complex act synergistically on the substrate, and the ligand can be deprotonated and dearomatized in situ in the reaction to generate active iridium catalytic species, and the transfer of hydrogen is achieved through the so-called proton response process.
  • the present invention has the following beneficial effects:
  • the ligand provided by the present invention can be deprotonated and dearomatized in situ to generate active iridium catalytic species during the reaction, and hydrogen transfer can be achieved through a proton response process.
  • the ligand and the metal part in the metal iridium complex provided by the present invention act synergistically on the substrate and have high catalytic performance in the "borrowing hydrogen" hydrogen transfer reaction.
  • the present invention can simply and quickly prepare a metal iridium complex having a proton response function from simple and readily available raw materials.
  • the complex can be dearomatized and re-aromatized in situ during the reaction, thereby avoiding the need to prepare dearomatized ligands in advance, thereby reducing the number of synthesis steps and improving ease of operation.
  • the synthesis of such ligands is simple and modular, which is conducive to the establishment of a ligand and complex library.
  • FIG1 is a single crystal structure of the metal iridium complex Cp*Ir-1.
  • FIG. 2 is a single crystal structure of the metal iridium complex Cp*Ir-2.
  • FIG3 is a single crystal structure of the metal iridium complex Cp*Ir-6.
  • This embodiment provides a ligand L-1 having a proton response function and a metal iridium complex Cp*Ir-1, and the preparation method is as follows:
  • Synthesis of ligand L-1 Add phenylboronic acid (1.5mmol) of the compound of formula I-1, 2-amino-6-bromopyridine (1mmol) of the compound of formula II-1, and palladium acetate (8.9mg, 4mol%) to a 50mL Schlenk tube, evacuate and replace nitrogen three times, and add 5mL of degassed water under nitrogen atmosphere. Under nitrogen range, the reaction temperature is 100°C, after 5h of reaction, cool to room temperature, add 30% NaOH aqueous solution to make pH>12, extract with ethyl acetate, add anhydrous sodium sulfate to the filtrate and dry, and evaporate the solvent in vacuum.
  • the crude product of compound III-1 is obtained without purification and directly proceeds to the next step.
  • the crude product was purified by column chromatography with petroleum ether/ethyl acetate (5:1) as the eluent to obtain a white solid L-1 with a yield of 90%.
  • This embodiment provides a ligand L-2 having a proton response function and a metal iridium complex Cp*Ir-2, and the reaction formula is as follows:
  • This embodiment provides a ligand L-3 having a proton response function and a metal iridium complex Cp*Ir-3, and the reaction formula is as follows:
  • This embodiment provides a ligand L-4 having a proton response function and a metal iridium complex Cp*Ir-4, and the reaction formula is as follows:
  • This embodiment provides a ligand L-5 having a proton response function and a metal iridium complex Cp*Ir-5, and the reaction formula is as follows:
  • This embodiment provides a ligand L-6 having a proton response function and a metal iridium complex Cp*Ir-6, and the reaction formula is as follows:
  • This embodiment provides a ligand L-7 having a proton response function and a metal iridium complex Cp*Ir-7, and the reaction formula is as follows:
  • This embodiment provides a ligand L-8 having a proton response function and a metal iridium complex Cp*Ir-8, and the reaction formula is as follows:
  • This embodiment provides a ligand L-9 having a proton response function and a metal iridium complex Cp*Ir-9, and the reaction formula is as follows:
  • This embodiment provides a ligand L-10 having a proton response function and a metal iridium complex Cp*Ir-10, and the reaction formula is as follows:
  • the present invention illustrates the process method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned process steps, that is, it does not mean that the present invention must rely on the above-mentioned process steps to be implemented.
  • Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

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Abstract

公开了一种具有质子响应功能的配体、金属铱络合物及其制备方法和应用，所述具有质子响应功能的配体具有如下式L所示的结构。从简单易得的原料出发可以简单快速的制备具有质子响应功能的金属铱络合物。该络合物在反应中可以原位进行去芳构化以及重新芳构化，从而可以避免预先制备去芳构化类型配体，达到减少合成步骤、提高操作简便性的目的;并且该类配体的合成简便，可模块化合成，利于建立配体和络合物库。公开的金属铱络合物在"借氢"氢转移反应中具有较高的催化性能。

Description

一种具有质子响应功能的配体、金属铱络合物及其制备方法和应用 技术领域
本发明属于金属有机领域，具体涉及一种具有质子响应功能的配体、金属铱络合物及其制备方法和应用，尤其涉及一种具有质子响应功能的配体、环戊二烯基金属铱络合物及其制备方法和应用。
背景技术
质子配体能够通过质子的获得或失去在两种不同的电子状态之间进行可逆的相互转换。配体控制质子响应单元的质子转移和金属中心的氢化物从合适的供体转移到受体。正因为此特点，含有这类配体的催化剂往往能有效应用于脱氢或借氢等氢化物和质子响应的反应中。质子响应单元的性质(酸碱性质)和配位方式是实现金属-配体协同的关键因素。
在探索此类催化剂的合成中，发现以吡啶基为核心单元，OH/＝O，CH 2/＝CH和NH/＝N为相互转换基团的金属络合物具有较好的催化活性。尤其是金属铱催化剂在相关的氢转移方面拥有优异的催化性能，例如如下式1和式2所示的金属铱催化剂：
Figure PCTCN2022137414-appb-000001
络合物1是由Yamaguchi在2012年首次报道，此类配合物通过质子响应，在芳基醇的脱氢反应中表现出优异的催化性能，该络合物通过配体与金属铱络合得到，再通过反应得到去芳构化的金属络合物。在反应过程中，通过与底物羟基反应，重构了配体中的芳构化，再脱氢进行去芳构化，完成催化循环。(Angew.Chem.Int.Ed.2012,51,12790)。该路线首先要合成金属前体1-2，然后与双氮配体络合得到中间体1-4，并在强碱作用下得到化合物1。
Figure PCTCN2022137414-appb-000002
文献报道络合物2的制备路线如下：从化合物2-1出发经过两步得到化合物2-3，化合物 2-3通过三步可以得到金属络合物2。上述要经过五步得到最终的金属络合物，并且在路线中还使用了有一定毒性的溴化苄。除此之外，在路线中还需要化学计量正丁基锂四氢呋喃溶液，反应操作和后处理比较繁琐。合成此络合物整体路线长，收率低，且生产成本高，产生废料多。
Figure PCTCN2022137414-appb-000003
以上两种络合物的配体在制备方面都存在一定的局限性，例如难以实现配体发散性合成，且配体的衍生相对困难，这导致催化剂的种类比较单一，难以建立催化剂库。
发明内容
针对现有技术的不足，本发明的目的在于提供一种具有质子响应功能的配体、金属铱络合物及其制备方法和应用。文献报道的合成此类性能的络合物路线和方法较为复杂，需预先制备去芳构化的金属络合物，在反应中实现重构芳构化，达到质子响应的功能，并且相关配体的合成方法较为复杂。本发明旨在发展一种新的配体及其铱金属络合物，从简单易得的原料出发可以简单快速的制备具有质子响应功能的铱金属络合物。该络合物在反应中可以原位进行去芳构化以及重新芳构化，从而可以避免预先制备去芳构化类型配体，达到减少合成步骤、提高操作简便性的目的。并且该类配体的合成简便，可模块化合成，利于建立配体和络合物库。
为达此目的，本发明采用以下技术方案：
第一方面，本发明提供一种具有质子响应功能的配体，所述具有质子响应功能的配体具有如下式L所示的结构：
Figure PCTCN2022137414-appb-000004
其中，R 1、R 2、R 3、R 4各自独立地选自氢、卤素、C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9、C10等)直链或支链烷基、C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9、C10等)烷氧基、卤素取代的C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9、C10等)烷基或-NR aR b中的任意一种；
R 5选自取代或未取代的C6-C12(例如可以是C6、C7、C8、C9、C10、C11、C12等)芳基、C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9、C10等)直链或支链烷基中的任意一种；
R a、R b各自独立地选自C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9、C10等)直链或支链烷基。
在本发明中，所述C6-C12芳基的取代基选自卤素、C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9、C10等)直链或支链烷基、C1-C10烷氧基(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9、C10等)、卤素取代的C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9、C10等)烷基或-NR cR d中的任意一种或至少两者的组合；R c、R d各自独立地选自C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9、C10等)直链或支链烷基(C6-C12芳基可以为单取代或多取代)。
在本发明中，所述R 1、R 2、R 3、R 4各自独立地选自氢、氟、甲基、乙基、丙基、异丙基、丁基、异丁基、正戊基、正己基、甲氧基、乙氧基、三氟甲基或-N(Me) 2中的任意一种。
优选地，所述R 5选自未取代或R e取代的苯基、C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9、C10等)直链或支链烷基中的任意一种，所述R e选自氢、氟、甲基、乙基、丙基、异丙基、丁基、异丁基、正戊基、正己基、甲氧基、乙氧基、三氟甲基或-N(Me) 2中的任意一种或至少两种的组合(苯基可以为单取代或多取代)。
优选地，所述具有质子响应功能的配体具有如下式L-1～L-10所示的结构：
Figure PCTCN2022137414-appb-000005
Figure PCTCN2022137414-appb-000006
第二方面，本发明提供一种根据第一方面所述具有质子响应功能的配体的制备方法，所述制备方法包括以下步骤：
(1)将式I所示化合物与式II所示化合物发生偶联反应，生成式III所示化合物，反应式如下所示：
Figure PCTCN2022137414-appb-000007
(2)将式III所示化合物与式IV所示化合物发生缩合反应，生成式L所示化合物，反应式如下所示：
Figure PCTCN2022137414-appb-000008
其中，R 1、R 2、R 3、R 4、R 5的限定范围与第一方面保持一致，X选自Cl、Br或I中的任意一种。
优选地，步骤(1)中，所述式I所示化合物与式II所示化合物的摩尔比为(1-2):1(其中，“1-2”可以是1、1.2、1.4、1.6、1.8、2等)。
优选地，步骤(1)中，所述偶联反应在催化剂存在下进行，所述催化剂包括醋酸钯和/或四(三苯基膦)钯。
优选地，所述式I所示化合物与催化剂的摩尔比为(30-45):1(其中，“30-45”可以是30、33、36、39、41、43、45等)。
优选地，步骤(1)中，所述偶联反应在脱气水中进行。
优选地，步骤(1)中，所述偶联反应的温度为90-110℃(例如可以是90℃、100℃、110℃等)，时间为4-6h(例如可以是4h、4.5h、5h、5.5h、6h等)。
在本发明中，步骤(2)中，所述式III所示化合物与式IV所示化合物的摩尔比为1:(1-1.2)(其中，“1-1.2”可以是1、1.05、1.1、1.15、1.2等)。
优选地，步骤(2)中，所述缩合反应在碱存在下进行，所述碱包括三乙胺、N,N-二异丙基乙胺或吡啶中的任意一种或至少两种的组合。
优选地，所述式III所示化合物与碱的摩尔比为1:(1.8-2.2)(其中，“1.8-2.2”可以是1.8、1.9、2、2.1、2.2等)。
优选地，步骤(2)中，所述缩合反应在有机溶剂中进行，所述有机溶剂包括二氯基烷、氯仿或甲苯中的任意一种或至少两种的组合。
优选地，步骤(2)中，所述缩合反应的温度为0-30℃(例如可以是0℃、5℃、10℃、15℃、20℃、25℃、30℃等)，时间为8-15h(例如可以是8h、9h、10h、11h、12h、13h、14h、15h等)。
第三方面，本发明提供一种具有质子响应功能的金属铱络合物，所述具有质子响应功能的金属铱络合物的配体选自根据第一方面所述具有质子响应功能的配体，所述具有质子响应功能的金属铱络合物具有如下式Cp*Ir所示的结构：
Figure PCTCN2022137414-appb-000009
其中，R 1、R 2、R 3、R 4、R 5的限定范围与第一方面保持一致。
在本发明中，所述具有质子响应功能的金属铱络合物具有如下式Cp*Ir-1～Cp*Ir-10所示的结构：
Figure PCTCN2022137414-appb-000010
第四方面，本发明提供一种根据第三方面所述的具有质子响应功能的金属铱络合物的制备方法，所述制备方法包括以下步骤：将式L所示化合物与[Cp*IrCl 2] 2发生络合反应，生成式Cp*Ir所示的金属铱络合物，反应式如下所示：
Figure PCTCN2022137414-appb-000011
其中，R 1、R 2、R 3、R 4、R 5的限定范围与第一方面保持一致。
在本发明中，所述式L所示化合物与[Cp*IrCl 2] 2的摩尔比为1:(0.2-0.5)(其中，“0.2-0.5”可以是0.2、0.3、0.4、0.5等)。
优选地，所述络合反应在碱存在下进行，所述碱包括醋酸钠、碳酸钠、醋酸钾或碳酸钾中的任意一种或至少两种的组合，优选为醋酸钠。
优选地，所述式L所示化合物与碱的摩尔比为1:(2-5)(其中，“2-5”可以是2、3、4、5等)。
优选地，所述络合反应在有机溶剂中进行，所述有机溶剂包括二氯甲烷、甲苯或四氢呋喃中的任意一种或至少两种的组合，优选为二氯甲烷。
优选地，所述络合反应的温度为20-30℃(例如可以是20℃、22℃、24℃、26℃、28℃、30℃等)，时间为20-30h(例如可以是20h、22h、24h、26h、28h、30h等)。
本发明通过采用商业可得硼酸、吡啶胺类化合物和金属铱前体，通过三步反应得到环戊二烯基铱络合物。并对其在醇脱氢方面催化性能进行相关的探索研究。通过此路线，提供一种具有质子响应功能金属铱络合物的制备方法，具有收率高、成本低、条件温和、工艺简单等优点。
本发明从简单易得的原料出发，通过三步可以制备具有质子响应功能的Cp*Ir金属络合物，对比相关文献报道的现有最好技术，具有起始原料经济、反应步骤少、操作相对简便、整体收率高等明显的优点，合成路线中没有涉及剧毒化学品，对环境相对友好和绿色。更重要的是，利用此方法可以模块化合成多样性配体，利于建立配体和络合物库，从而提高其在有机合成中的广谱性。
第五方面，本发明提供一种根据第一方面所述的具有质子响应功能的配体或根据第三方面所述的具有质子响应功能的金属铱络合物在催化氢转移反应中的应用。
优选地，所述氢转移反应包括醇氢转移反应。
优选地，所示醇氢转移反应包括苯乙酮与苄基醇的α烷基化反应或芳烃与苄基醇的烷基化反应。
本发明提供的金属铱络合物在催化酮或烯烃的烷基化反应中具有较高的催化性能。该络合物的配体和金属部分协同作用于底物，配体能够在反应中原位脱质子去芳构化生成活性铱催化物种，通过所谓的质子响应过程来实现氢的转移。
相对于现有技术，本发明具有以下有益效果：
(1)本发明提供的配体能够在反应中原位脱质子去芳构化生成活性铱催化物种，通过质子响应过程来实现氢的转移。
(2)本发明提供的金属铱络合物中配体和金属部分协同作用于底物，在“借氢”氢转移反应中具有较高的催化性能。
(3)本发明从简单易得的原料出发可以简单快速的制备具有质子响应功能的金属铱络合物。该络合物在反应中可以原位进行去芳构化以及重新芳构化，从而可以避免预先制备去芳构化类型配体，达到减少合成步骤、提高操作简便性的目的。并且该类配体的合成简便，可模块化合成，利于建立配体和络合物库。
附图说明
图1为金属铱络合物Cp*Ir-1的单晶结构。
图2为金属铱络合物Cp*Ir-2的单晶结构。
图3为金属铱络合物Cp*Ir-6的单晶结构。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1
本实施例提供一种具有质子响应功能的配体L-1和金属铱络合物Cp*Ir-1，制备方法如下：
Figure PCTCN2022137414-appb-000012
配体L-1的合成：将式I-1化合物苯硼酸(1.5mmol)、式II-1化合物2-氨基-6-溴吡啶(1mmol)以及醋酸钯(8.9mg,4mol％)加入到50mL Schlenk管中，抽真空置换氮气三次，在氮气氛围下，加入脱气水5mL。氮气范围下，反应温度100℃，反应5h后，冷至室温，加入30％NaOH水溶液，使PH>12，用乙酸乙酯萃取，滤液加入无水硫酸钠干燥，溶剂真空蒸发。得到化合物III-1粗产物无需纯化，直接进行下一步。将化合物III-1加入50mL反应瓶中，加入10mL DCM，保持0℃，并将式IV-1化合物苯甲酰氯(1.1equiv)、三乙胺(2.0equiv)缓慢加入到上述溶液中，搅拌10h后，加入NaHCO 3饱和溶液淬灭反应，用DCM萃取，滤液加入无水 硫酸钠干燥，溶剂真空蒸发。粗产物使用柱层析提纯，洗脱剂为石油醚/乙酸乙酯(5:1)。最终得到白色固体L-1，产率90％。
1H NMR(400MHz,CDCl 3):δ8.72(s,1H),8.34(d,J＝8.4Hz,1H),7.98-7.94(m,4H),7.84(t,J＝8.0Hz,1H),7.58(t,J＝7.2Hz,1H),7.54-7.42(m,6H)； 13C NMR(100MHz,CDCl 3):165.9,156.2,151.4,139.4,138.8,134.5,132.4,129.3,129.0,128.9,127.3,127.0,116.9,112.6.
金属铱络合物Cp*Ir-1的合成：将配体L-1(0.055mmol)、[Cp*IrCl 2] 2(0.02mmol)以及醋酸钠(0.2mmol)加入到10mL Schlenk管中，加入DCM 3mL，室温条件下反应24h。反应完成后，溶剂真空蒸发，粗产物使用柱层析进行分离提纯，洗脱剂为石油醚/乙酸乙酯(3:1)，随后溶剂真空蒸发，得到黄色固体，产率91％。
1H NMR(400MHz,CDCl 3):δ10.69(s,1H),8.26(d,J＝8.0Hz,2H),8.22(d,J＝8.0Hz,1H),7.80(d,J＝8.0Hz,1H),7.47(t,J＝8.0Hz,1H),7.57-7.66(m,5H),7.23(t,J＝8.0Hz,1H),7.07(t,J＝8.0Hz,1H),1.40(s,15H)； 13C NMR(100MHz,CDCl 3):166.1,165.5,163.8,152.6,145.2,139.2,136.5,133.6,132.8,130.8,129.0,128.3,124.1,122.5,113.5,112.2,89.3,8.9.
实施例2
本实施例提供一种具有质子响应功能的配体L-2和金属铱络合物Cp*Ir-2，反应式如下：
Figure PCTCN2022137414-appb-000013
配体L-2和金属铱络合物Cp*Ir-2的制备方法同实施例1。
配体L-2：产率89％； 1H NMR(400MHz,CDCl 3):δ8.84(s,1H),8.35(d,J＝8.4Hz,1H),7.92(d,J＝7.2Hz,2H),7.82(t,J＝8.0Hz,1H),7.56-7.53(m,2H),7.50-7.46(m,4H),7.37(t,J＝8.0Hz,1H),6.97(dd,J 1＝8.0Hz,J 2＝2.8Hz,1H),3.86(s,3H)； 13C NMR(100MHz,CDCl 3):166.0,160.2,155.8,151.4,140.2,139.4,134.4,132.3,129.9,128.9,127.3,119.3,116.9,115.1,112.8,112.3,55.5.
金属铱络合物Cp*Ir-2：产率67％； 1H NMR(400MHz,CDCl 3):δ10.88(s,1H),8.29(d,J＝7.2Hz,2H),8.17(dd,J 1＝8.0Hz,J 2＝1.2Hz,1H),7.75(t,J＝8.0Hz,1H),7.64(t,7.2Hz,1H),7.56-7.64(m,3H),7.33(dd,J 1＝8.0Hz,J 2＝1.2Hz,1H),7.06(t,J＝8.0Hz,1H),6.79(dd,J 1＝8.0Hz,J 2＝1.2Hz,1H),3.88(s,3H),1.40(s,15H)； 13C NMR(100MHz,CDCl 3):166.4,165.6,162.8,152.8,152.6,146.4,139.1,133.5,132.8,128.9,128.3,123.9,118.1,114.0,113.3,112.6,89.5,56.7,8.8.
实施例3
本实施例提供一种具有质子响应功能的配体L-3和金属铱络合物Cp*Ir-3，反应式如下：
Figure PCTCN2022137414-appb-000014
配体L-3和金属铱络合物Cp*Ir-3的制备方法同实施例1。
配体L-3：产率91％； 1H NMR(400MHz,CDCl 3):δ8.76(s,1H),8.29(d,J＝8.0Hz,1H),7.93(d,J＝7.6Hz,2H),7.80(t,J＝8.0Hz,1H),7.58-7.55(m,2H),7.52-7.46(m,4H),6.95(d,J＝8.4Hz,1H),3.97(s,3H),3.94(s,3H)； 13C NMR(100MHz,CDCl 3):166.0,155.8,151.3,150.2,149.3,139.3,134.5,132.3,131.7,128.9,127.3,119.6,116.3,112.0,111.2,109.9,56.1,56.1.
金属铱络合物Cp*Ir-3：产率95％； 1H NMR(400MHz,CDCl 3):δ10.62(s,1H),8.26(d,J＝7.2Hz,2H),8.13(d,J＝8.0Hz,1H),7.69(t,J＝8.0Hz,1H),7.56-7.64(m,3H),7.42(dd,J 1＝7.6Hz,J 2＝0.8Hz,1H),7.30(s,1H),7.16(s,1H),4.05(s,3H),3.93(s,3H),1.41(s,15H)； 13C NMR(100MHz,CDCl 3):166.1,165.5,156.4,152.4,151.3,145.7,139.1,136.6,133.7,132.8,128.9,128.2,118.1,112.8,110.8,108.2,89.1,56.2,55.8,8.9.
实施例4
本实施例提供一种具有质子响应功能的配体L-4和金属铱络合物Cp*Ir-4，反应式如下：
Figure PCTCN2022137414-appb-000015
配体L-4和金属铱络合物Cp*Ir-4的制备方法同实施例1。
配体L-4：产率83％； 1H NMR(400MHz,CDCl 3):δ8.77(s,1H),8.40(d,J＝8.0Hz,1H),8.28(s,1H),8.12(d,J＝7.6Hz,1H),7.95(d,J＝7.2Hz,2H),7.86(t,J＝7.6Hz,1H),7.67(d,J＝8.0Hz,1H),7.58-7.49(m,5H)； 13C NMR(100MHz,CDCl 3):166.0,154.3,151.7,139.6,139.5,134.3,132.5,131.3(q,J＝27.0Hz),130.0,139.3,129.0(q,J＝2.0Hz),127.4,125.8(q,J＝4.0Hz),125.7,123.9(q,J＝4.0Hz),122.9,116.7,113.4； 19F NMR(376MHz,CDCl 3):-62.6.
金属铱络合物Cp*Ir-4：产率89％； 1H NMR(400MHz,CDCl 3):δ10.64(s,1H),8.29(dd,J 1＝8.4Hz,J 2＝1.6Hz,1H),8.24(dd,J 1＝8.0Hz,J 2＝1.2Hz,2H),7.92(d,J＝7.6Hz,1H),7.80-7.84(m,2H),7.65(d,J＝8.0Hz,2H),7.60(t,J＝8.0Hz,2H),7.44(dd,J 1＝8.0Hz,J 2＝2.5Hz,1H),1.41(s,15H)； 13C NMR(100MHz,CDCl 3):169.5,165.5,164.7,152.9,145.7,139.6,136.9,133.4,133.0,129.0,128.2,126.6(q,3.0Hz),125.2,124.9,123.6,120.4(q,3.9Hz),113.8,113.2,89.8,8.9； 19F NMR(376MHz,CDCl 3):-61.8.
实施例5
本实施例提供一种具有质子响应功能的配体L-5和金属铱络合物Cp*Ir-5，反应式如下：
Figure PCTCN2022137414-appb-000016
配体L-5和金属铱络合物Cp*Ir-5的制备方法同实施例1。
配体L-5：产率80％； 1H NMR(400MHz,CDCl 3):δ9.38(s,1H),8.38(d,J＝8.0Hz,1H),7.90-7.87(m,2H),7.83(t,J＝8.0Hz,1H),7.45-7.38(m,3H),7.54-7.50(m,2H),7.34(t,J＝8.0Hz,1H),7.27-7.24(m,1H),6.82(dd,J 1＝8.0Hz,J 2＝2.4Hz,1H),2.97(s,6H)； 13C NMR(100MHz,CDCl 3):166.3,157.0,151.6,139.5,139.3,134.4,132.0,129.5,128.7,127.3,117,1,115.4,113.6,113.7,112.7,111.1,40.6.
金属铱络合物Cp*Ir-5：产率77％； 1H NMR(400MHz,CDCl 3):δ10.72(s,1H),8.26(dd,J 1＝8.4Hz,J 2＝1.2Hz,1H),8.21(d,J＝8.0Hz,2H),7.74(t,J＝8.0Hz,1H),7.55-7.64(m,5H),7.13(s,1H),6.94(dd,J 1＝8.4Hz,J 2＝2.8Hz,1H),2.97(s,6H),1.40(s,15H)； 13C NMR(100MHz,CDCl 3):166.4,165.5,152.5,145.1,139.0,136.5,133.7,132.8,128.9,128.3,118.9,113.4,112.0,89.0,42.0,8.9.
实施例6
本实施例提供一种具有质子响应功能的配体L-6和金属铱络合物Cp*Ir-6，反应式如下：
Figure PCTCN2022137414-appb-000017
配体L-6和金属铱络合物Cp*Ir-6的制备方法同实施例1。
配体L-6：产率88％； 1H NMR(400MHz,CDCl 3):δ8.62(s,1H),8.32(d,J＝8.0Hz,1H),7.97(d,J＝8.0Hz,2H),7.92(d,J＝9.2Hz,2H),7.81(t,J＝8.0Hz,1H),7.40-7.50(m,4H),6.99(d,J＝8.8Hz,2H),3.88(s,1H)； 13C NMR(100MHz,CDCl 3):165.4,162.9,156.1,151.6,139.3,138.9,129.3,129.2,128.9,127.0,126.6,116.6,114.2,112.5,55.6.
金属铱络合物Cp*Ir-6：产率89％； 1H NMR(400MHz,CDCl 3):δ10.57(s,1H),8.26(d,J＝8.8Hz,2H),8.21(d,J＝8.0Hz,1H),7.78(dd,J 1＝7.6Hz,J 2＝1.2Hz,1H),7.71(t,J＝8.0Hz,1H),7.60(dd,J 1＝7.6Hz,J 2＝1.2Hz,1H),7.54(dd,J 1＝8.0Hz,J 2＝1.2Hz,1H),7.21(td,J 1＝7.2Hz,J 2＝1.2Hz,1H),7.02-7.07(m,3H),3.90(s,6H),1.40(s,15H)； 13C NMR(100MHz,CDCl 3):165.9,165.0,163.7,163.2,152.8,145.2,139.1,136.5,130.7,130.3,125.8,124.1,122.5,114.1,113.2,112.1,89.3,55.5,8.9.
实施例7
本实施例提供一种具有质子响应功能的配体L-7和金属铱络合物Cp*Ir-7，反应式如下：
Figure PCTCN2022137414-appb-000018
配体L-7和金属铱络合物Cp*Ir-7的制备方法同实施例1。
配体L-7：产率89％； 1H NMR(600MHz,CDCl 3):δ9.09(s,1H),8.33(d,J＝8.4Hz,1H),7.95(d,J＝7.8Hz,2H),7.90(dd,J 1＝8.4Hz,J 2＝1.8Hz,2H),7.85(t,J＝7.8Hz,1H),7.69(d,J＝7.8Hz,2H),7.51(d,J＝7.2Hz,1H),7.46-7.41(m,3H)； 13C NMR(150MHz,CDCl 3):164.9,156.3,151.3,139.6,138.6,137.7,133.8(q,J＝33Hz),129.4,128.9,127.8,126.9,125.9(q,J＝3.0Hz),123.7(q,J＝271.5Hz),117.2,112.7； 19F NMR(376MHz,CDCl 3):-63.0.
金属铱络合物Cp*Ir-7：产率90％； 1H NMR(400MHz,CDCl 3):δ10.75(s,1H),8.32(d,J＝8.0Hz,2H),8.12(dd,J 1＝8.0Hz,J 2＝1.2Hz,1H),7.78(d,J＝8.0Hz,2H),7.77-7.66(m,2H),7.55-7.50(m,2H),7.15(td,J 1＝7.6Hz,J 2＝1.2Hz,1H),6.98(td,J 1＝7.6Hz,J 2＝1.2Hz,1H),1.37(s,15H)； 13C NMR(100MHz,CDCl 3): 13C NMR(150MHz,CDCl 3):166.3,163.9(d,J＝10Hz),152.2,145.0,139.4,136.8,136.5,134.5,134.2,130.9,128.8,126.0(q,J＝3.6Hz),125.0,124.3,122.6,122.3,113.8,112.0,89.3,8.9； 19F NMR(376MHz,CDCl 3):-63.0.
实施例8
本实施例提供一种具有质子响应功能的配体L-8和金属铱络合物Cp*Ir-8，反应式如下：
Figure PCTCN2022137414-appb-000019
配体L-8和金属铱络合物Cp*Ir-8的制备方法同实施例1。
配体L-8：产率89％； 1H NMR(400MHz,CDCl 3):δ9.87(s,1H),8.34(d,J＝8.0Hz,1H),7.92(d,J＝8.0Hz,1H),7.85-7.81(m,2H),7.56(d,J＝8.0Hz,1H),7.48-7.44(m,3H)； 13C NMR(150MHz,CDCl 3):154.8,154.7,150.2,139.3,138.4,136.2,129.1,128.8,128.0,127.9,125.3,119.6,119.4,116.1,112.2； 19F NMR(376MHz,CDCl 3):-139.8(d,J＝18.8Hz),-150.9(t,J＝22.6Hz),-159.8(td,J 1＝22.6Hz,J 2＝7.5Hz).
金属铱络合物Cp*Ir-8：产率87％； 1H NMR(400MHz,CDCl 3):δ10.65(s,1H),8.11(dd,J 1 ＝8.0Hz,J 2＝1.2Hz,1H),7.78-7.74(m,2H),7.62(t,J＝8.0Hz,2H),7.21(dd,J 1＝7.2Hz,J 2＝1.2Hz,1H),7.06(td,J 1＝7.6Hz,J 2＝1.6Hz,1H),1.44(s,15H)； 13C NMR(100MHz,CDCl 3):166.7,164.3,155.8,151.6,145.1,144.8,143.4,139.6,138.6,138.5,136.9,130.9,129.0,126.9,124.5,122.6,114.5,112.2,89.1,8.6； 19F NMR(376MHz,CDCl 3):-139.8(d,J＝14.6Hz),-148.4(t,J＝21.1Hz),-158.7(td J 1＝20.3Hz,J 2＝5.6Hz).
实施例9
本实施例提供一种具有质子响应功能的配体L-9和金属铱络合物Cp*Ir-9，反应式如下：
Figure PCTCN2022137414-appb-000020
配体L-9和金属铱络合物Cp*Ir-9的制备方法同实施例1。
配体L-9：产率87％ 1H NMR(400MHz,CDCl 3):δ9.12(s,1H),8.43(d,J＝8.0Hz,1H),7.94(d,J＝8.0Hz,2H),7.82(t,J＝8.0Hz,1H),7.47-7.41(m,4H),7.14(t,J＝7.6Hz,1H),6.90(d,J＝8.0Hz,2H),2.20(s,6H)； 13C NMR(100MHz,CDCl 3):169.3,155.5,151.5,139.5,138.1,137.1,133.9,129.2,128.8,128.7,127.6,126.7,116.4,112.4,19.1.
金属铱络合物Cp*Ir-9：产率89％； 1H NMR(400MHz,CDCl 3):δ7.91(dd,J 1＝8.0Hz,J 2＝2.4Hz,2H),7.48-7.47(m,3H),7.25-7.18(m,2H),7.09-7.04(m,2H),6.71(d,J＝7.6Hz,1H),5.09(d,J＝8.4Hz,1H),2.36(s,3H),2.29(s,3H),1.55(s,15H)； 13C NMR(100MHz,CDCl 3):172.1,167.6,156.0,140.4,138.8,138.6,134.3,132.6,129.5,129.2,128.8,128.4,128.2,127.6,115.3,110.2,85.7,19.2,9.9.
实施例10
本实施例提供一种具有质子响应功能的配体L-10和金属铱络合物Cp*Ir-10，反应式如下：
Figure PCTCN2022137414-appb-000021
配体L-10和金属铱络合物Cp*Ir-10的制备方法同实施例1。
配体L-10：产率89％ 1H NMR(400MHz,CDCl 3):δ8.24(s,1H),8.15(d,J＝8.0Hz,1H),7.93(d,J＝8.8Hz,2H),7.77(t,J＝8.0Hz,1H),7.48-7.41(m,4H),2.15(s,3H)； 13C NMR(100MHz,CDCl 3):168.9,155.9,151.2,139.3,138.8,129.2,128.8,126.8,116.5,112.2,24.7.
金属铱络合物Cp*Ir-10：产率89％； 1H NMR(400MHz,CDCl3):δ10.01(s,1H),8.05(d,J＝8.8Hz,1H),7.75(dd,J 1＝7.6Hz,J 2＝1.2Hz,1H),7.65(t,J＝8.0Hz,1H),7.56(dd,J 1＝7.6Hz,J 2＝1.2Hz,1H),7.49(dd,J 1＝7.6Hz,J 2＝1.2Hz,1H),7.18(td,J 1＝7.2Hz,J 2＝1.2Hz,1H),7.02(td,J 1＝7.6Hz,J 2＝1.2Hz,1H),2.30(s,3H),1.52(s,15H)； 13C NMR(100MHz,CDCl3):168.7,165.9,163.8,152.3,145.2,139.3,136.7,130.7,124.2,122.6,113.4,111.7,89.2,25.2,8.9.
应用例1
Cp*Ir催化苯乙酮与苄基醇的α烷基化反应
在氮气氛围下，向10个10mL Schlenk分别加入化合物1(1.0mmol)、化合物2(1.1mmol)、氢氧化钾(10mol％)、超干甲苯1mL以及不同的Cp*Ir金属络合物(0.05mol％)，在油浴加热130℃，反应50min后停止反应，将溶剂旋蒸干，得到的粗产品通过柱层析进行分离提纯，得到淡黄色油状液体(化合物3)。
Figure PCTCN2022137414-appb-000022
化合物3： 1H NMR(400MHz,CDCl 3)δ＝7.90(d,J＝8.0Hz,2H),7.55(t,J＝7.8Hz,1H),7.48(t,J＝7.8Hz,2H),7.18-7.23(m,5H),3.27(t,J＝8.0Hz,2H),2.98(t,J＝7.8Hz,2H)； 13C (100MHz,CDCl 3)δ＝199.3,141.2,136.9,133.1,128.7,128.6,128.5,128.1,126.2,40.6,30.6.
采用不同催化剂催化苯乙酮与苄基醇的α烷基化反应，转化率和产率统计结果如下表1所示：
表1
Figure PCTCN2022137414-appb-000023
Figure PCTCN2022137414-appb-000024
由表1数据可知，采用本发明提供的Cp*Ir催化苯乙酮与苄基醇的α烷基化反应，具有较高的转化率和收率。
应用例2
Cp*Ir催化茚与伯醇的烷基化反应
在氮气氛围下，向10个10mL Schlenk分别加入化合物4(1.0mmol)、化合物5(1.1mmol)、叔丁醇钾(15mol％)、超干甲苯1mL以及不同的Cp*Ir金属络合物(1mol％)中，在油浴 加热130℃，反应8h后停止反应，将溶剂旋蒸干，得到的粗产品通过柱层析进行分离提纯，得到无色液体。
Figure PCTCN2022137414-appb-000025
化合物6： 1H NMR(400MHz,CDCl 3)δ7.45(d,J＝7.6Hz,1H),7.36(d,J＝7.6Hz,1H),7.29(t,J＝7.2Hz,1H),7.19(t,J＝7.6,1H),6.11(t,J＝8.0Hz 1H),3.32(d,J＝4.8Hz,2H),2.58-2.53(m,2H),1.69-1.65(m,2H),1.46-1.41(m,2H),0.96(t,J＝7.4Hz,3H). 13C NMR(100MHz,CDCl 3):δ145.8,144.9,144.7,127.7,126.0,124.7,123.9,119.0,37.8,30.4,27.6,22.9,14.2.
化合物7： 1H NMR(400MHz,CDCl 3)δ7.52-7.50(m,1H),7.32-7.36(m,3H)6.13-6.11(m,1H),3.90-3.85(m,1H),2.62(t,J＝8.0Hz,2H),1.87-1.80(m,1H),1.75-1.67(m,1H),1.61-1.56(m,1H),1.55-1.50(m,1H),1.11-0.99(m,5H),0.88-0.72(m,6H)； 13C NMR(100MHz,CDCl 3):δ147.4,145.9,145.6,126.8,126.5,124.6,123.0,119.6,51.2,32.1,32.0,30.2,29.0,22.4,22.3,14.0,13.9
采用不同催化剂催化芳烃与伯醇的烷基化反应，转化率和产率统计结果如下表2所示：
表2
Figure PCTCN2022137414-appb-000026
Figure PCTCN2022137414-appb-000027
Figure PCTCN2022137414-appb-000028
由表1数据可知，采用本发明提供的Cp*Ir催化芳烃与伯醇的烷基化反应，具有较高的转化率和收率。
结构鉴定1(金属铱络合物Cp*Ir-1)
Figure PCTCN2022137414-appb-000029
金属铱络合物Cp*Ir-1的单晶结构如图1所示，主要参数如下表3所示：
表3
Figure PCTCN2022137414-appb-000030
Figure PCTCN2022137414-appb-000031
结构鉴定2(金属铱络合物Cp*Ir-2)
Figure PCTCN2022137414-appb-000032
金属铱络合物Cp*Ir-2的单晶结构如图2所示，主要参数如下表4所示：
表4
Figure PCTCN2022137414-appb-000033
Figure PCTCN2022137414-appb-000034
结构鉴定3(金属铱络合物Cp*Ir-6)
Figure PCTCN2022137414-appb-000035
金属铱络合物Cp*Ir-6的单晶结构如图3所示，主要参数如下表5所示：
表5
Figure PCTCN2022137414-appb-000036
Figure PCTCN2022137414-appb-000037
申请人声明，本发明通过上述实施例来说明本发明的工艺方法，但本发明并不局限于上述工艺步骤，即不意味着本发明必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种具有质子响应功能的配体，其特征在于，所述具有质子响应功能的配体具有如下式L所示的结构：
    Figure PCTCN2022137414-appb-100001
    其中，R 1、R 2、R 3、R 4各自独立地选自氢、卤素、C1-C10直链或支链烷基、C1-C10烷氧基、卤素取代的C1-C10烷基或-NR aR b中的任意一种；
    R 5选自取代或未取代的C6-C12芳基、C1-C10直链或支链烷基中的任意一种；
    R a、R b各自独立地选自C1-C10直链或支链烷基。
  2. 根据权利要求1所述的具有质子响应功能的配体，其特征在于，所述C6-C12芳基的取代基选自卤素、C1-C10直链或支链烷基、C1-C10烷氧基、卤素取代的C1-C10烷基或-NR cR d中的任意一种或至少两者的组合；R c、R d各自独立地选自C1-C10直链或支链烷基。
  3. 根据权利要求1或2所述的具有质子响应功能的配体，其特征在于，所述R 1、R 2、R 3、R 4各自独立地选自氢、氟、甲基、乙基、丙基、异丙基、丁基、异丁基、正戊基、正己基、甲氧基、乙氧基、三氟甲基或-N(Me) 2中的任意一种；
    优选地，所述R 5选自未取代或R e取代的苯基、C1-C10直链或支链烷基中的任意一种，所述R e选自氢、氟、甲基、乙基、丙基、异丙基、丁基、异丁基、正戊基、正己基、甲氧基、乙氧基、三氟甲基或-N(Me) 2中的任意一种或至少两种的组合；
    优选地，所述具有质子响应功能的配体具有如下式L-1～L-10所示的结构：
    Figure PCTCN2022137414-appb-100002
  4. 一种根据权利要求1-3任一项所述具有质子响应功能的配体的制备方法，其特征在于，所述制备方法包括以下步骤：
    (1)将式I所示化合物与式II所示化合物发生偶联反应，生成式III所示化合物，反应式如下所示：
    Figure PCTCN2022137414-appb-100003
    (2)将式III所示化合物与式IV所示化合物发生缩合反应，生成式L所示化合物，反应式如下所示：
    Figure PCTCN2022137414-appb-100004
    其中，R 1、R 2、R 3、R 4、R 5的限定范围与权利要求1-3任一项保持一致，X选自Cl、Br或I中的任意一种。
  5. 根据权利要求4所述的制备方法，其特征在于，步骤(1)中，所述式I所示化合物与式II所示化合物的摩尔比为(1-2):1；
    优选地，步骤(1)中，所述偶联反应在催化剂存在下进行，所述催化剂包括醋酸钯和/或四(三苯基膦)钯；
    优选地，所述式I所示化合物与催化剂的摩尔比为(30-45):1；
    优选地，步骤(1)中，所述偶联反应在脱气水中进行；
    优选地，步骤(1)中，所述偶联反应的温度为90-110℃，时间为4-6h；
    优选地，步骤(2)中，所述式III所示化合物与式IV所示化合物的摩尔比为1:(1-1.2)；
    优选地，步骤(2)中，所述缩合反应在碱存在下进行，所述碱包括三乙胺、N,N-二异丙基乙胺或吡啶中的任意一种或至少两种的组合；
    优选地，所述式III所示化合物与碱的摩尔比为1:(1.8-2.2)；
    优选地，步骤(2)中，所述缩合反应在有机溶剂中进行，所述有机溶剂包括二氯甲烷、氯仿或甲苯中的任意一种或至少两种的组合；
    优选地，步骤(2)中，所述缩合反应的温度为0-30℃，时间为8-15h。
  6. 一种具有质子响应功能的金属铱络合物，其特征在于，所述具有质子响应功能的金属铱络合物的配体选自根据权利要求1-3任一项所述具有质子响应功能的配体，所述具有质子响应功能的金属铱络合物具有如下式Cp*Ir所示的 结构：
    Figure PCTCN2022137414-appb-100005
    其中，R 1、R 2、R 3、R 4、R 5的限定范围与权利要求1-3任一项保持一致。
  7. 根据权利要求6所述的具有质子响应功能的金属铱络合物，其特征在于，所述具有质子响应功能的金属铱络合物具有如下式Cp*Ir-1～Cp*Ir-10所示的结构：
    Figure PCTCN2022137414-appb-100006
    Figure PCTCN2022137414-appb-100007
  8. 一种根据权利要求6或7所述的具有质子响应功能的金属铱络合物的制备方法，其特征在于，所述制备方法包括以下步骤：将式L所示化合物与[Cp*IrCl 2] 2发生络合反应，生成式Cp*Ir所示的金属铱络合物，反应式如下所示：
    Figure PCTCN2022137414-appb-100008
    其中，R 1、R 2、R 3、R 4、R 5的限定范围与权利要求1-3任一项保持一致。
  9. 根据权利要求8所述的制备方法，其特征在于，所述式L所示化合物与[Cp*IrCl 2] 2的摩尔比为1:(0.2-0.5)；
    优选地，所述络合反应在碱存在下进行，所述碱包括醋酸钠、碳酸钠、醋酸钾或碳酸钾中的任意一种或至少两种的组合，优选为醋酸钠；
    优选地，所述式L所示化合物与碱的摩尔比为1:(2-5)；
    优选地，所述络合反应在有机溶剂中进行，所述有机溶剂包括二氯甲烷、甲苯或四氢呋喃中的任意一种或至少两种的组合，优选为二氯甲烷；
    优选地，所述络合反应的温度为20-30℃，时间为20-30h。
  10. 一种根据权利要求1-3任一项所述的具有质子响应功能的配体或根据权利要求6或7所述的具有质子响应功能的金属铱络合物在催化氢转移反应中的应用；
    优选地，所述氢转移反应包括醇氢转移反应；
    优选地，所示醇氢转移反应包括苯乙酮与苄基醇的α烷基化反应或芳烃与苄基醇的烷基化反应。
PCT/CN2022/137414 2022-11-18 2022-12-08 一种具有质子响应功能的配体、金属铱络合物及其制备方法和应用 Ceased WO2024103458A1 (zh)

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CN104804041A (zh) * 2014-01-26 2015-07-29 中国科学院上海有机化学研究所 Ncp配体、其铱络合物、合成方法、中间体及应用

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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE Registry 28 August 2008 (2008-08-28), ANONYMOUS: "Benzamide, N-(6-phenyl-2-pyridiny l)-", XP093172017, Database accession no. 1044239-11-3 *
HEITMAN LAURA H., VAN VELDHOVEN JACOBUS P. D., ZWEEMER ANNELIEN M., YE KAI, BRUSSEE JOHANNES, IJZERMAN ADRIAAN P.: "False Positives in a Reporter Gene Assay: Identification and Synthesis of Substituted N -Pyridin-2-ylbenzamides as Competitive Inhibitors of Firefly Luciferase", JOURNAL OF MEDICINAL CHEMISTRY, AMERICAN CHEMICAL SOCIETY, US, vol. 51, no. 15, 1 August 2008 (2008-08-01), US , pages 4724 - 4729, XP093091151, ISSN: 0022-2623, DOI: 10.1021/jm8004509 *
ZENG ZHENG, DENG YIQIU; LI LANYU; LI CHUNGANG; ZHONG MINGLI: "Hydrogen Transfer Coupling with 100% Atom Economy: Synthesis of 2-Indolyltetrahydronaphthyridine Derivatives", THE JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, vol. 87, no. 18, 16 September 2022 (2022-09-16), pages 12257 - 12264, XP093172021, ISSN: 0022-3263, DOI: 10.1021/acs.joc.2c01436 *

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