CN112390831B - Triplecene ring metal palladium compound and application thereof - Google Patents
Triplecene ring metal palladium compound and application thereof Download PDFInfo
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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
- 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
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
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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
- 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
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
- B01J2231/4227—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with Y= Cl
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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
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
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- B01J2531/824—Palladium
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Abstract
The invention discloses a tricyclene ring metal palladium compound and application thereof, wherein the tricyclene ring metal palladium compound has the following general formula:
wherein: three R A May be the same or different and each independently represents R 1 ‑(Z 1 ‑A 1 ‑Z 2 ) x -; three R B May be the same or different and each independently represents R 2 ‑(Z 3 ‑A 2 ‑Z 4 ) y -; two R C May be the same or different and each independently represents R 3 ‑(Z 5 ‑A 3 ‑Z 6 ) z -. The tricyclene ring metal palladium compound provided by the invention has a large sterically hindered group of tricyclene, can stabilize a zero-valent palladium intermediate in catalytic cycle, improves catalytic efficiency, reduces the usage amount of a catalyst to less than one ten thousandth, has simple synthesis steps, high yield and low cost, is suitable for various substrates, and has important application value for researching the progress and application of coupling reaction.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a tricyclene ring metal palladium compound and application thereof.
Background
Suzuki coupling reaction of aryl boric acid and halogenated hydrocarbon plays an important role in organic synthesis. In the past decades, the reaction has the advantages of mild reaction conditions, wide substrate application range, no toxic and harmful byproducts, easy product treatment and the like, so that the reaction is widely applied to the fields of laboratory research, pharmaceutical industry and fine chemical industry and is used for synthesizing various types of organic compounds.
Catalysts commonly used for Suzuki reaction include metallic palladium catalysts and metallic nickel catalysts, wherein the metallic palladium catalysts have been widely studied and applied because they can be applied to aqueous systems and can endure many types of functional groups, while the nickel catalysts must be anhydrous and anaerobic conditions in the reaction.
Palladium metal Suzuki reaction catalysts comprise many types including cyclic palladium compound systems, palladium compound systems containing bulky hindered phosphine ligands or electron rich ligands, palladium compound systems containing nucleophilic N-heterocyclic carbenes, water soluble palladium catalytic systems, phosphine ligand free palladium catalytic systems, and the like. The cyclic palladium compound system has high stability to air and heat, is easy to recycle in catalytic reaction, has high activity, and some mature systems can catalyze the coupling of activated and non-activated chlorobenzene and phenylboronic acid under mild conditions, so that the catalytic system of the type is widely researched
Although the research on the Suzuki reaction catalyst has been greatly advanced, the application of the Suzuki reaction catalyst in industry still has many problems and defects, such as the Suzuki reaction catalyst cannot be applied to various substrates, and the Suzuki reaction catalyst has high content, high cost, difficult long-term storage and the like. Therefore, the metal catalyst with high stability, high activity, wide substrate application range, recyclability, low cost and high molecular conversion number (TON) and molecular conversion frequency (TOF) is still important research content.
Accordingly, there is a need for a metal catalyst that meets the above requirements and its use in coupling reactions.
Disclosure of Invention
The invention aims to provide a tricycloalkene ring metal palladium compound and application thereof, which are used for solving the problems in the prior art and can provide a ring metal palladium catalyst with high stability, high activity and wide substrate application range.
The invention provides a tricyclene ring metal palladium compound, which has the following general formula:
three R A May be the same or different and each independently represents R 1 -(Z 1 -A 1 -Z 2 ) x -；
Three R B May be the same or different and each independently represents R 2 -(Z 3 -A 2 -Z 4 ) y -；
Two R C May be the same or different and each independently represents R 3 -(Z 5 -A 3 -Z 6 ) z -。
The tripropenyl cyclometalated palladium compound as described above, wherein R is preferably 1 、R 2 、R 3 Each independently selected from-H, -Cl, -CN, -CF 3 、-OCF 3 Any one of an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms, a fluorinated alkyl group having 1 to 15 carbon atoms, a fluorinated alkoxy group having 1 to 15 carbon atoms and a fluorinated linear alkenyl group having 2 to 15 carbon atoms.
Three as described aboveA cycloalkene metal palladium compound, wherein, preferably, Z 1 、Z 2 、Z 3 、 Z 4 、Z 5 、Z 6 Each independently selected from-O-, -S-, -OCO-, -COO-, -CO-, -CH 2 O-、-OCH 2 -、 -OCF 2 Any one of a linear alkyl group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms, a linear alkynyl group having 2 to 15 carbon atoms, a fluorinated linear alkyl group having 1 to 15 carbon atoms, a fluorinated alkenyl group having 2 to 15 carbon atoms and a carbon-carbon single bond.
The tripropenyl cyclometalated palladium compound as described above, wherein, preferably, A 1 、A 2 、A 3 Each independently selected from 1, 4-cyclohexylene, 1, 4-phenylene, diphenylphosphino, N-phenyl-carbazol-2-yl, N-phenyl-carbazol-3-yl, 9, 10-anthracenyl, 1-naphthyl, 2-naphthyl, 4-triphenylamino, 2, 5-pyrimidyl, any one of 3, 9-carbazolyl, 2, 5-pyridyl, 2, 5-tetrahydro-2H-pyranyl, 1, 3-dioxan-2, 5-yl, 1,2, 4-oxadiazol-3, 5-yl, fluorinated 1, 4-cyclohexylene, fluorinated pyran ring diyl, cyclic lactone diyl, five-membered oxaheterocyclic diyl, five-membered thiaheterocyclic diyl or five-membered azaheterocyclic diyl, and a carbon-carbon single bond.
The tris-cyclopentadienyl ring metal palladium compound as described above, wherein x, y, z each independently represent an integer of 0 to 3, is preferred.
The tris (cyclopentadienyl) cyclometallated palladium compound as described above, wherein, when x, y and Z each independently represent any integer between 0 and 3, the structural unit Z is preferably 1 -A 1 -Z 2 In, Z 1 Identical or different, A 1 Same or different, Z 2 The same or different; structural unit Z 3 -A 2 -Z 4 In, Z 3 Same or different, A 2 Same or different, Z 4 The same or different; structural unit Z 5 -A 3 -Z 6 In Z 5 Identical or different, A 3 Same or different, Z 6 The same or different.
The tripropenyl ring metallic palladium compound as described above, wherein, preferably, X represents any one of F, Cl, Br and I atoms.
The application of the tricycloalkene ring metal palladium compound is to be applied to Suzuki coupling reaction or Buchwald-Hartwig coupling reaction.
The use of the tricycloalkene ring palladium compound as described above, wherein it is preferred that the tricycloalkene ring palladium compound has the following general formula:
three R A May be the same or different and each independently represents R 1 -(Z 1 -A 1 -Z 2 ) x -；
Three R B May be the same or different and each independently represents R 2 -(Z 3 -A 2 -Z 4 ) y -；
Two R C May be the same or different and each independently represents R 3 -(Z 5 -A 3 -Z 6 ) z -。
Use of the tripropenyl ring metallic palladium compound as described above, wherein, preferably, R is 1 、R 2 、 R 3 Each independently selected from-H, -Cl, -CN, -CF 3 、-OCF 3 Any one of an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms, a fluorinated alkyl group having 1 to 15 carbon atoms, a fluorinated alkoxy group having 1 to 15 carbon atoms and a fluorinated linear alkenyl group having 2 to 15 carbon atoms.
The invention provides a tricyclene ring metal palladium compound, which has a large sterically hindered group of tricyclene, can stabilize a zero-valent palladium intermediate in catalytic cycle, improves catalytic efficiency, reduces the usage amount of a catalyst to less than one ten thousandth, has simple synthesis steps, high yield and low cost, is suitable for various substrates, and has important application value for researching the progress and application of coupling reaction.
Detailed Description
Various exemplary embodiments of the present disclosure will now be described in detail. The description of the exemplary embodiments is merely illustrative and is in no way intended to limit the disclosure, its application, or uses. The present disclosure may be embodied in many different forms and is not limited to the embodiments described herein. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. It should be noted that: the relative arrangement of parts and steps, the composition of materials, numerical expressions and numerical values set forth in these embodiments are to be construed as merely illustrative, and not as limitative, unless specifically stated otherwise.
"first", "second" used in the present disclosure: and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The word "comprising" or "comprises", and the like, means that the element preceding the word covers the element listed after the word, and does not exclude the possibility that other elements are also covered. "upper", "lower", and the like are used only to indicate relative positional relationships, and when the absolute position of the object being described is changed, the relative positional relationship may also be changed accordingly.
In the present disclosure, when a specific component is described as being located between a first component and a second component, there may or may not be intervening components between the specific component and the first component or the second component. When it is described that a specific component is connected to other components, the specific component may be directly connected to the other components without having an intervening component, or may be directly connected to the other components without having an intervening component.
All terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs unless specifically defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Techniques, methods and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate.
Example 1
The tripropenyl ring palladium metal compound provided in this example has the following general formula:
three R A May be the same or different and each independently represents R 1 -(Z 1 -A 1 -Z 2 ) x -；
Three R B May be the same or different and each independently represents R 2 -(Z 3 -A 2 -Z 4 ) y -；
Two R C May be the same or different and each independently represents R 3 -(Z 5 -A 3 -Z 6 ) z -。
Further, R 1 、R 2 、R 3 Each independently selected from-H, -Cl, -CN, -CF 3 、-OCF 3 Any one of an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms, a fluorinated alkyl group having 1 to 15 carbon atoms, a fluorinated alkoxy group having 1 to 15 carbon atoms and a fluorinated linear alkenyl group having 2 to 15 carbon atoms.
Further, Z 1 、Z 2 、Z 3 、Z 4 、Z 5 、Z 6 Each independently selected from-O-, -S-, -OCO-, -COO-, -CO-, -CH 2 O-、-OCH 2 -、-OCF 2 Any one of a linear alkyl group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms, a linear alkynyl group having 2 to 15 carbon atoms, a linear alkyl group having 1 to 15 fluorinated carbon atoms, a fluorinated alkenyl group having 2 to 15 carbon atoms and a carbon-carbon single bond.
Further, A 1 、A 2 、A 3 Each independently selected from 1, 4-cyclohexylene, 1, 4-phenylene, diphenylphosphino, N-phenyl-carbazol-2-yl, N-phenyl-carbazol-3-yl, 9, 10-anthracenyl, 1-naphthyl, 2-naphthyl, 4-triphenylamino, 2, 5-pyrimidyl, any one of 3, 9-carbazolyl, 2, 5-pyridyl, 2, 5-tetrahydro-2H-pyranyl, 1, 3-dioxan-2, 5-yl, 1,2, 4-oxadiazol-3, 5-yl, fluorinated 1, 4-cyclohexylene, fluorinated pyran ring diyl, cyclic lactone diyl, five-membered oxazacyclo-diyl, five-membered thiazacyclo-diyl or five-membered azacyclo-diyl, and a carbon-carbon single bond.
Further, x, y, z each independently represent an integer between 0 and 3. And, when x, y and Z each independently represent an integer of 0 to 3, the structural unit Z 1 -A 1 -Z 2 In, Z 1 Identical or different, A 1 Same or different, Z 2 The same or different; structural unit Z 3 -A 2 -Z 4 In, Z 3 Identical or different, A 2 Same or different, Z 4 The same or different; structural unit Z 5 -A 3 -Z 6 In, Z 5 Identical or different, A 3 Same or different, Z 6 The same or different.
Further, X represents any one of F, Cl, Br, and I atoms.
EXAMPLE 2 preparation of Compound 1
Firstly, 9-amido triptycene is utilized to synthesize a compound 1a through metal coordination reaction, and then the synthesized compound 1a is utilized to obtain a compound 1 through ligand exchange reaction, wherein the specific structure of the compound 1 is as follows.
Specifically, when Compound 1a was synthesized, 73mg (0.27mmol) of 9-aminotridecene and 67mg (0.27mmol) of Li were charged in a 100mL two-necked flask 2 PdCl 4 22mg (0.27mmol) NaOAc, 15mL methanol, reacted at room temperature for 2h, successively dried with oxygen and solventThe procedure of alumina column chromatography and methanol elution gave 55mg of compound 1a as a yellow solid in 52% yield.
The synthesis of compound 1a is as follows:
when Compound 1 was synthesized from Compound 1a, 100mg (0.08mmol) of Compound 1a and 64mg (0.24mmol) of PPh were added to a 100mL two-necked flask 3 (triphenylphosphine) and 15mL dichloromethane react for 2h at room temperature, and the light yellow solid of the compound 1, 158mg and 98% yield, are obtained after the steps of draining the solvent, carrying out alumina column chromatography and eluting dichloromethane in sequence.
The synthesis reaction of compound 1 is as follows:
EXAMPLE 3 preparation of Compound 2
Compound 1a synthesized by reaction formula (1) is subjected to a ligand exchange reaction to obtain compound 2, and the specific structure of compound 2 is as follows.
Specifically, when Compound 2 was synthesized from Compound 1a, 100mg (0.08mmol) of Compound 1a and 68mg (0.24mmol) of PCy were added to a 100mL two-necked flask 3 (tricyclohexylphosphine) and 15mL of dichloromethane react for 2h at room temperature, and the light yellow solid of the compound 2 is obtained in the amount of 156mg in a yield of 94% after the steps of solvent extraction, alumina column chromatography and dichloromethane leaching.
The synthesis reaction of compound 2 is as follows:
EXAMPLE 4 preparation of Compound 3
Firstly, a compound 3b is synthesized by a compound 3a through a metal coordination reaction, and then a compound 3 is obtained by the synthesized compound 3b through a ligand exchange reaction, wherein the specific structure of the compound 3 is as follows.
Specifically, when Compound 3b was synthesized, 84mg (0.27mmol) of Compound 3a and 119mg (0.27mmol) of Li were charged into a 100mL two-necked flask 2 PdCl 4 22mg (0.27mmol) of NaOAc and 15mL of methanol are reacted for 2h at room temperature, and the yellow solid 89mg of the compound 3b is obtained by the steps of draining the solvent, performing alumina column chromatography and eluting with methanol in sequence, wherein the yield is 66%.
The synthesis of compound 3b is as follows:
when compound 3 is synthesized from compound 3b, 120mg (0.08mmol) of compound 3b, 64mg (0.24mmol) of PPh3 and 15mL of dichloromethane are added into a 100mL two-necked flask, and the mixture is reacted for 2h at room temperature, and then the steps of draining the solvent, performing alumina column chromatography and eluting with dichloromethane are sequentially performed to obtain 164mg of compound 3 as a pale yellow solid with the yield of 90%.
The synthesis reaction of compound 3 is as follows:
EXAMPLE 5 preparation of Compound 4
Firstly, a compound 4b is synthesized by a compound 4a through a metal coordination reaction, and then a compound 4 is obtained by the synthesized compound 4b through a ligand exchange reaction, wherein the specific structure of the compound 4 is as follows.
Specifically, when Compound 4b was synthesized, 139mg (0.27mmol) of Compound 4a and 119mg (0.27mmol) of Li were charged into a 100mL two-necked flask 2 PdCl 4 22mg (0.27mmol) of NaOAc and 15mL of methanol are reacted at room temperature for 2h, and then the yellow solid of the compound 4b is obtained by the steps of draining the solvent, performing alumina column chromatography and eluting with methanol, wherein the yield is 72%.
The synthesis of compound 4b is as follows:
when Compound 4 was synthesized from Compound 4b, 158mg (0.08mmol) of Compound 4b and 64mg (0.24mmol) of PPh were added to a 100mL two-necked flask 3 And 15mL of dichloromethane, reacting for 2h at room temperature, and sequentially performing the steps of solvent pumping, alumina column chromatography and dichloromethane leaching to obtain 208mg of a light yellow solid of the compound 4 with the yield of 94%.
The synthesis reaction of compound 4 is as follows:
EXAMPLE 6 preparation of Compound 5
Firstly, a compound 5b is synthesized by utilizing a compound 5a through a metal coordination reaction, and then a compound 5 is obtained by utilizing the synthesized compound 5b through a ligand exchange reaction, wherein the specific structure of the compound 5 is as follows.
Specifically, when Compound 5b was synthesized, 102mg (0.27mmol) of Compound 5a and 119mg (0.27mmol) of Li were charged into a 100mL two-necked flask 2 PdCl 4 22mg (0.27mmol) of NaOAc, 15mL of methanol at room temperatureAnd reacting for 2 hours, and sequentially performing solvent pumping, alumina column chromatography and methanol leaching to obtain 77mg of yellow solid of the compound 5b, wherein the yield is 55%.
The synthesis of compound 5b is as follows:
when Compound 5 was synthesized from Compound 5b, 158mg (0.08mmol) of Compound 5b and 64mg (0.24mmol) of PPh were added to a 100mL two-necked flask 3 And 15mL of dichloromethane, reacting for 2h at room temperature, and sequentially performing the steps of solvent pumping, alumina column chromatography and dichloromethane leaching to obtain 351mg of a light yellow solid of the compound 5 with the yield of 94%.
The synthesis reaction of compound 5 is as follows:
example 7 comparative testing of catalyst Performance
1.5mmol of substituted phenylboronic acid, 1.1mmol of potassium tert-butoxide (t-BuOK) and 1.0mmol of a Pd catalyst (compound 1, compound 2, compound 3, compound 4, compound 5 and compound 6 respectively) are sequentially added into a Schlenk tube containing magnetons, then 1.0mmol of substituted halobenzene and 1mL of a solvent (i-PrOH, isopropanol) are added, and stirring is carried out at 80 ℃ for 2h (the conditions are the optimal reaction conditions for the general reaction formula (10)). Then dissolved in dichloromethane and mixed with alumina, column chromatographed (eluent dichloromethane/petroleum ether 2:1) to give the colorless substituted biphenyl product, weighed and the yield calculated.
Among them, the compounds 1 to 5 were synthesized in examples 2 to 6 of the present invention, and the compound 6 was a comparative example having a composition of Pd (PPh) 3 ) 2 Cl 2 The catalyst is a commercial general catalyst at present. The difference between the compound 1 and the compound 5 is that in the general formula of the palladium compound of the tricyclene ring metal provided by the invention, R A 、R B 、R C And X is taken separatelyThe compound obtained by different structural units has the following reaction formula:
the reaction results are shown in Table 1 below, in Table 1, test numbers 1 to 9 correspond to 9 combinations of substituted halogenobenzenes and substituted phenylboronic acids in the above reaction formula (10), respectively, and R is 1 The columns represent R in substituted halogenobenzenes 1 Corresponding radical structural units, in which o represents ortho-substitution, m represents meta-substitution, p represents para-substitution, R 2 The column indicates R in the substituted phenylboronic acid 2 Corresponding group structural units (both are-H), the column of X represents the group structural unit corresponding to X in the substituted halogenobenzene, and the substituted halogenobenzene and substituted phenylboronic acid adopted in the test numbers 1-9 can be directly purchased commercially. Yield 1 is listed as the yield of the catalytic reaction using compound 1 as a Pd catalyst, yield 2 is listed as the yield of the catalytic reaction using compound 2 as a Pd catalyst, and so on.
TABLE 1 results of comparative testing of catalyst Performance
As can be seen from Table 1, the palladium compounds (compound 1-compound 5) of the present invention as catalysts have very good catalytic effects on different substrates (test No. 1-test No. 9) under optimum conditions (stirring at 80 ℃ for 2 h). It can be seen that the catalytic system has a very high yield for reactions containing electron donating groups on the benzene ring (test No. 1-test No. 3, test No. 5 and test No. 6); when the benzene ring contained an electron-withdrawing group, the yield was slightly lowered (test No. 4 and test No. 7). And for different substrates, the method has higher yield and wide applicability. The yield was improved to some extent as compared with the comparative example (Compound 6), and the catalytic effect was very good also for the chlorinated aromatic compounds which were difficult to perform (test No. 8 to test No. 9), which was not achieved by the comparative example. The reason is that the tridentate alkene ring metal palladium compound of the invention introduces the tridentate alkene steric hindrance group, can stabilize the zero-valent palladium intermediate in the catalytic cycle, and improves the catalytic efficiency.
Example 8 catalytic comparison of aromatic chlorine with aromatic boric acid
1.5mmol of substituted aromatic boric acid, 1.1mmol of potassium tert-butoxide (t-BuOK) and 1.0 mmol% of Pd catalyst (compound 1, compound 2, compound 3, compound 4, compound 5 and compound 6 respectively) are sequentially added into a Schlenk tube containing magnetons, then 1.0mmol of substituted aromatic chlorine and 1mL of solvent (i-PrOH, isopropanol) are added, and stirring is carried out at 80 ℃ for 2 h. Then dissolved in dichloromethane and mixed with alumina, column chromatography (eluent dichloromethane/petroleum ether 2:1) is carried out to obtain colorless products, and the yield is calculated after weighing.
Among them, the compounds 1 to 5 were synthesized in examples 2 to 6 of the present invention, and the compound 6 was a comparative example having a composition of Pd (PPh) 3 ) 2 Cl 2 The reaction formula is as follows:
wherein X, Y represents O, N, S or P atom, and n and m represent an integer of 1-6;
as shown in Table 2 below, in Table 2, test Nos. 10 to 15 correspond to 9 combinations of the substituted aromatic chlorine and the substituted aromatic boronic acid in the above reaction formula (11), respectively, the column in which the aromatic chlorine is present indicates what structure the substituted aromatic chlorine is, the column in which the aromatic boronic acid is present indicates what structure the substituted aromatic boronic acid is, and the substituted aromatic chlorine and the substituted aromatic boronic acid used in test Nos. 10 to 15 are commercially available. Yield 1 is listed as the yield of the catalytic reaction using the compound 1 as a Pd catalyst, and yield 2 is listed as the yield of the catalytic reaction using the compound 2 as a Pd catalyst.
TABLE 2 catalytic comparison of aromatic chlorine with aromatic boric acid test results
As can be seen from Table 2, the palladium trispiralene ring metal compounds (compounds 1 to 5) of the present invention have better catalytic effects on various aromatic chlorine substrates and aromatic boric acid under the optimal conditions (stirring at 80 ℃ for 2h) and even can catalyze the coupling of chlorinated alkane and aromatic boric acid (test No. 14), while the catalytic efficiency of the comparative example (compound 6) is very low, even lower than 10%, while the Suzuki coupling reaction of chlorinated aromatic hydrocarbon substrates has a great development prospect in synthesis and is one of the key difficulties of the Suzuki coupling reaction, which cannot be realized by the comparative example.
Example 9 experimental comparison of catalyst amounts
1.5mmol of phenylboronic acid, 1.1mmol of potassium tert-butoxide (t-BuOK) and Pd catalysts (compound 1, compound 2, compound 3, compound 4, compound 5 and compound 6 respectively) in different proportions are sequentially added into a Schlenk tube filled with magnetons, then 1.0mmol of p-methoxybromobenzene and 1mL of solvent (i-PrOH, isopropanol) are added, and the mixture is stirred for 2 hours at the temperature of 80 ℃. Then dissolving with dichloromethane, adding alumina, performing column chromatography (eluent dichloromethane/petroleum ether is 2:1) to obtain a colorless product, weighing, and calculating the yield.
Among them, the compounds 1 to 5 were synthesized in examples 2 to 6 of the present invention, and the compound 6 was a comparative example having a composition of Pd (PPh) 3 ) 2 Cl 2 The reaction formula is as follows:
the reaction results are shown in the following table 3, in table 3, test numbers 16 to 21 correspond to different catalyst amounts, the column of yield 1 shows the yield of the catalytic reaction using the compound 1 as a Pd catalyst, the column of yield 2 shows the yield of the catalytic reaction using the compound 2 as a Pd catalyst, and so on.
TABLE 3 results of catalyst testing
As can be seen from table 3, the tricycloalkene metal palladium compound of the present invention (compound 1 to compound 5) can catalyze the reaction with a very high yield using only four parts per million as compared with the comparative example (compound 6) as a catalyst, which can catalyze the reaction only at a thousandth of the amount, and the amount of the catalyst has a very large influence on the cost control of raw materials and the ease of post-treatment in industrial production, so that the tricycloalkene metal palladium compound of the present invention has a great advantage in the cost control of mass production, which cannot be achieved by the comparative example.
In conclusion, compared with the conventional metal palladium catalyst, the tricycloalkene ring metal palladium compound disclosed by the invention has a better catalytic effect on the Suzuki reaction, has good universal applicability on reaction substrates with various different substituents, can catalyze the coupling reaction of chlorinated aromatic hydrocarbon at high yield, has a remarkable advantage in the dosage of the catalyst, can ensure the catalytic reaction only by four ten-thousandth of dosage, is simple and convenient in synthesis method, has higher yield and higher popularization and application values, and cannot be realized by the conventional metal palladium catalyst.
Example 10
The invention also provides an application of the tricyclene ring metal palladium compound, and the tricyclene ring metal palladium compound is applied to Suzuki coupling reaction or Buchwald-Hartwig coupling reaction.
Further, the tripropenyl ring metal palladium compound has the following general formula:
three R A May be the same or different and each independently represents R 1 -(Z 1 -A 1 -Z 2 ) x -；
Three R B May be the same or different and each independently represents R 2 -(Z 3 -A 2 -Z 4 ) y -；
Two R C May be the same or different and each independently represents R 3 -(Z 5 -A 3 -Z 6 ) z -。
Further, R 1 、R 2 、R 3 Each independently selected from-H, -Cl, -CN, -CF 3 、-OCF 3 Any one of an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms, a fluorinated alkyl group having 1 to 15 carbon atoms, a fluorinated alkoxy group having 1 to 15 carbon atoms and a fluorinated linear alkenyl group having 2 to 15 carbon atoms.
Further, Z 1 、Z 2 、Z 3 、Z 4 、Z 5 、Z 6 Each independently selected from-O-, -S-, -OCO-, -COO-, -CO-, -CH 2 O-、-OCH 2 -、-OCF 2 Any one of a linear alkyl group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms, a linear alkynyl group having 2 to 15 carbon atoms, a linear alkyl group having 1 to 15 fluorinated carbon atoms, an alkenyl group having 2 to 15 fluorinated carbon atoms and a carbon-carbon single bond.
Further, A 1 、A 2 、A 3 Each independently selected from 1, 4-cyclohexylene, 1, 4-phenylene, diphenylphosphino, N-phenyl-carbazol-2-yl, N-phenyl-carbazol-3-yl, 9, 10-anthracenyl, 1-naphthyl, 2-naphthyl, 4-triphenylamino, 2, 5-pyrimidyl, any one of 3, 9-carbazolyl, 2, 5-pyridyl, 2, 5-tetrahydro-2H-pyranyl, 1, 3-dioxan-2, 5-yl, 1,2, 4-oxadiazol-3, 5-yl, fluorinated 1, 4-cyclohexylene, fluorinated pyran ring diyl, cyclic lactone diyl, five-membered oxazacyclo-diyl, five-membered thiazacyclo-diyl or five-membered azacyclo-diyl, and a carbon-carbon single bond.
Further, x,y and z each independently represent an integer of 0 to 3. And, when x, y and Z each independently represent an integer of 0 to 3, the structural unit Z 1 -A 1 -Z 2 In, Z 1 Identical or different, A 1 Same or different, Z 2 The same or different; structural unit Z 3 -A 2 -Z 4 In, Z 3 Identical or different, A 2 Same or different, Z 4 The same or different; structural unit Z 5 -A 3 -Z 6 In, Z 5 Same or different, A 3 Same or different, Z 6 The same or different.
Further, X represents any one of F, Cl, Br, and I atoms.
The tricyclene ring metal palladium compound provided by the embodiment of the invention has a large sterically hindered group of tricyclene, can stabilize a zero-valent palladium intermediate in catalytic cycle, improves catalytic efficiency, reduces the usage amount of a catalyst to less than one ten thousand, has simple synthesis steps, high yield and low cost, is suitable for various substrates, and has important application value for researching the progress and application of coupling reaction.
Thus, various embodiments of the present disclosure have been described in detail. Some details well known in the art have not been described in order to avoid obscuring the concepts of the present disclosure. It will be fully apparent to those skilled in the art from the foregoing description how to practice the presently disclosed embodiments.
Although some specific embodiments of the present disclosure have been described in detail by way of example, it should be understood by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the present disclosure. It will be understood by those skilled in the art that various changes may be made in the above embodiments or equivalents may be substituted for elements thereof without departing from the scope and spirit of the present disclosure. The scope of the present disclosure is defined by the appended claims.
Claims (2)
1. A tripsacene ring metal palladium compound, shown as follows:
2. use of the tripropenyl ring metallic palladium compound of claim 1, characterized in that the tripropenyl ring metallic palladium compound is applied in a Suzuki coupling reaction.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003013723A1 (en) * | 2001-08-10 | 2003-02-20 | Ciba Speciality Chemicals Holding Inc. | Palladium catalysts |
| WO2011127579A1 (en) * | 2010-04-14 | 2011-10-20 | Kanata Chemical Technologies Inc. | Cationic palladium complexes comprising diamino carbene ligands and their use in catalysis |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003013723A1 (en) * | 2001-08-10 | 2003-02-20 | Ciba Speciality Chemicals Holding Inc. | Palladium catalysts |
| WO2011127579A1 (en) * | 2010-04-14 | 2011-10-20 | Kanata Chemical Technologies Inc. | Cationic palladium complexes comprising diamino carbene ligands and their use in catalysis |
Non-Patent Citations (3)
| Title |
|---|
| 《High-Activity Catalysts for Suzuki Coupling and Amination Reactions with Deactivated Aryl Chloride Substrates: Importance of the Palladium Source》;Robin B. Bedford等;《Organometallics》;20030201;第22卷(第5期);第987-999页 * |
| 《Simple mixed tricyclohexylphosphane-triarylphosphite complexes as extremely high-activity catalysts for the Suzuki coupling of aryl chlorides》;Bedford, Robin B等;《Angewandte Chemie, International Edition》;20021231;第41卷(第21期);第4120-4122页 * |
| 《The role of ligand transformations on the performance of phosphite- and phosphinite-based palladium catalysts in the Suzuki reaction》;Bedford, Robin B等;《Organometallics》;20030222;第22卷(第7期);第1364-1371页 * |
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