CN116789710A - Metal compound containing tri-dish alkene carbene structure and application thereof - Google Patents
Metal compound containing tri-dish alkene carbene structure and application thereof Download PDFInfo
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- 150000002736 metal compounds Chemical class 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical group [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 19
- 150000001336 alkenes Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 3
- 238000007341 Heck reaction Methods 0.000 claims description 3
- 238000006411 Negishi coupling reaction Methods 0.000 claims description 3
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 23
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 239000000543 intermediate Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 4
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- LNJXVUXPFZKMNF-UHFFFAOYSA-K iridium(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Ir](Cl)Cl LNJXVUXPFZKMNF-UHFFFAOYSA-K 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- TYLYVJBCMQFRCB-UHFFFAOYSA-K trichlororhodium;trihydrate Chemical compound O.O.O.[Cl-].[Cl-].[Cl-].[Rh+3] TYLYVJBCMQFRCB-UHFFFAOYSA-K 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DBENTMPUKROOOE-UHFFFAOYSA-N 2-naphthalen-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=C(C=CC=C2)C2=C1 DBENTMPUKROOOE-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- 238000007125 Buchwald synthesis reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VFHDCDDYMMQCBF-UHFFFAOYSA-M [Cl-].[Zn+]C1=CC=CC=C1 Chemical compound [Cl-].[Zn+]C1=CC=CC=C1 VFHDCDDYMMQCBF-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000006352 cycloaddition reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a metal compound containing a tri-dish alkene-carbene structure and application thereofThe object structure is as follows:the catalyst has the advantages of simple preparation, high yield, suitability for various substrates when being used as a catalyst, great reduction of the catalyst consumption, and good catalytic effect on various metal catalyzed reactions. Has important application value for researching the progress and application of catalytic reaction.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a metal compound containing a tri-dish alkene carbene structure and application thereof.
Background
The metal catalyst has rich reactivity, plays an important role in organic synthesis, and becomes the most widely used catalyst in various organic chemical reactions such as hydrogenation, coupling, cycloaddition and the like. In the past decades, due to the advantages of mild reaction conditions, wider application range of substrates, non-toxic byproducts, easy product treatment and the like, the metal catalyst is widely applied to the fields of laboratory research and fine chemical industry in the pharmaceutical industry and is used for synthesizing various types of organic compounds.
Taking the Suzuki reaction as an example, the Suzuki reaction is one of the most commonly used aromatic ring coupling reactions, wherein the most commonly used catalyst is a metal palladium catalyst, and the catalytic system of the type is widely studied, and the palladium metal catalyst has relatively high stability to air and heat, is easy to recycle in the catalytic reaction, has high activity, and some of more mature systems can catalyze the coupling of chlorobenzene and phenylboronic acid under relatively mild conditions, so that the catalyst becomes one of the most important means of modern organic synthesis and is applied to the field of synthesis of a plurality of organic molecules.
Despite the great progress in the research of metal catalysts, there are still many problems and drawbacks in the industrial application thereof. Because of the high price, for many ligands and catalyst systems, the problems of complex structure, harsh preparation conditions, easy deactivation, difficult recycling after reaction and the like exist, so that the metal catalyst with high stability, high activity, wide substrate application range, recyclability, low manufacturing cost and high TON and TOF is still an important research content.
Disclosure of Invention
The invention aims to solve the technical problems that the metal catalyst used in the prior organic reaction cannot be suitable for various substrates, the catalyst content is high, the cost is high, the long-time storage is difficult, and the like.
The invention adopts the following technical scheme to solve the technical problems: there is provided a metal compound comprising a tri-discoene carbene structure, the structure being,
，
including R1, R2, R3, R4, R5, R6, R7, R8, M.
Preferably, the method comprises the steps of, the R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from any one of-H, -D, -T, -Cl, -F, -CN, -CD3, -CF3, -OCF3, substituted or unsubstituted alkyl group with carbon number of 1-15, substituted or unsubstituted alkoxy group with carbon number of 1-15, linear substituted or unsubstituted olefin group with carbon number of 2-15, substituted or unsubstituted alkyl group with carbon number of 1-15, fluorinated alkoxy group with carbon number of 1-15, linear substituted or unsubstituted alkylene group with carbon number of 2-15, substituted or unsubstituted aryl group with carbon number of 5-20, substituted or unsubstituted heteroaryl group with carbon number of 5-20, substituted or unsubstituted condensed ring aryl group with carbon number of 5-20 or substituted or unsubstituted condensed ring aryl group with carbon number of 5-20.
Preferably, M represents Ir or Rh.
Preferably, the triptycene carbene allylpalladium compound of claim 1 is used in a catalyst for the Suzuki reaction, buchwald-Hartwig reaction, heck reaction, still reaction or Negishi reaction.
Use of a metal compound comprising a tri-discoene carbene structure, characterized in that: the use of a metal compound according to claim 1, which contains a tri-discoene carbene structure, in a catalyst.
Compared with the prior art, the invention provides a metal compound containing a tri-dish alkene carbene structure and application thereof, and the metal compound has the following beneficial effects: the preparation is simple and convenient, the yield is high, the catalyst is suitable for various substrates when used as a catalyst, the use amount of the catalyst can be greatly reduced, and the catalyst has better catalytic effect on various metal catalyzed reactions. Has important application value for researching the progress and application of catalytic reaction.
Drawings
FIG. 1 is a diagram of the structure of a metal compound of the present invention;
FIG. 2 is a diagram of the Cat-001 architecture of the present invention;
FIG. 3 is a view showing the construction of Cat-002;
FIG. 4 is a diagram of Cat-003;
FIG. 5 is a diagram of the Cat-004 structure of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation methods in the technical scheme are conventional methods unless otherwise specified, and raw materials can be obtained from public commercial sources unless otherwise specified.
EXAMPLE 1 preparation of Compound Cat-001
To a 500mL two-necked flask, 3.7g (10.0 mmol) of Cat-001a,100mL of tetrahydrofuran was added, the mixture was cooled to 0℃in an ice bath, 15mL (2.0 mol/L) of a hexane solution of butyllithium was slowly dropped, 3.5g (10.0 mmol) of iridium trichloride trihydrate was added after the completion of the dropping, the reaction was continued at 0℃for 1 hour, then 3.1g (20.0 mmol) of 2-phenylpyridine was added, the reaction was gradually carried out to room temperature for 2 hours, the solvent was removed under reduced pressure, alumina column chromatography, petroleum ether: ethyl acetate=1:1 elution gave 7.6g of yellow solid in 91% yield.
Elemental analysis (for C46H34IrN 4), theory: c,66.17; h,4.10; n,6.71. Actual measurement value: c,66.33; h,4.15; n,6.64.
Mass spectrometry (ESI): m/z 834.23 (M+).
EXAMPLE 2 preparation of Compound Cat-002
To a 500mL two-necked flask, 4.3g (10.0 mmol) of Cat-002a,100mL of tetrahydrofuran was added, the mixture was cooled to 0℃in an ice bath, 15mL (2.0 mol/L) of a hexane solution of butyllithium was slowly dropped, 3.5g (10.0 mmol) of iridium trichloride trihydrate was added after the completion of the dropping, the reaction was maintained at 0℃for 1 hour, then 1.6g (10.0 mmol) of 2-phenylpyridine and 2.1g (10.0 mmol) of 2-naphthylpyridine were added, the mixture was gradually warmed to room temperature and reacted for 2 hours, the solvent was dried under reduced pressure, alumina column chromatography, petroleum ether: ethyl acetate=1:1 elution afforded 8.1g of yellow solid in 86% yield.
Elemental analysis (for C55H38IrN 4), theory: c,69.75; h,4.04; n,5.92. Actual measurement value: c,69.46; h,4.10; n,5.74.
Mass spectrometry (ESI): m/z 946.26 (M+).
EXAMPLE 3 Synthesis of Compound Cat-003
To a 500mL two-necked flask, 4.5g (10.0 mmol) of Cat-003a,100mL of tetrahydrofuran was added, the mixture was cooled to 0℃in an ice bath, 15mL (2.0 mol/L) of a hexane solution of butyllithium was slowly added dropwise, 2.6g (10.0 mmol) of rhodium trichloride trihydrate was added after the completion of the dropwise addition, the mixture was allowed to react at 0℃for 1 hour, then 4.0g (20.0 mmol) of Cat-003b was added, the mixture was gradually warmed to room temperature and reacted for 2 hours, the solvent was removed under reduced pressure, alumina column chromatography and petroleum ether: ethyl acetate=1:1 elution gave 8.4g of yellow solid in 92% yield.
Elemental analysis (for C53H46F2N4O2 Rh), theoretical: c,69.81; h,5.08; n,6.14. Actual measurement value: c,69.97; h,5.10; n,6.22.
Mass spectrometry (ESI): m/z 910.26 (M+).
EXAMPLE 4 Synthesis of Compound Cat-004
To a 500mL two-necked flask, 4.1g (10.0 mmol) of Cat-004a,100mL of tetrahydrofuran was added, the mixture was cooled to 0℃in an ice bath, 15mL (2.0 mol/L) of a hexane solution of butyllithium was slowly dropped, 2.6g (10.0 mmol) of rhodium trichloride trihydrate was added after the completion of the dropping, the reaction was carried out at 0℃for 1 hour, then 1.8g (10.0 mmol) of Cat-004b and 2.6g (10.0 mmol) of Cat-004c were added, the reaction was gradually carried out to room temperature for 2 hours, the solvent was removed under reduced pressure, alumina column chromatography, petroleum ether: ethyl acetate=1:1 elution gave 8.2g of yellow solid in 90% yield.
Elemental analysis (for C58H45N5 Rh), theoretical: c,76.14; h,4.96; n,7.65. Actual measurement value: c,76.02; h,5.08; n,7.66.
Mass spectrometry (ESI): m/z 913.26 (M+).
Example 5 catalytic comparison of Suzuki coupling reactions
To a Schlenk tube containing a magneton, 1.5mmol of phenylboronic acid, 1.1mmol of potassium tert-butoxide and 0.01% mmol of catalyst (compounds Cat-001, cat-002, cat-003, cat-004, 1) were successively added, followed by 1.0mmol of p-methoxybromobenzene, 1mL of isopropanol and stirring at 80℃for 2 hours. Then, after dissolution with dichloromethane, alumina was added and column chromatography (eluent dichloromethane/petroleum ether=2:1) to give a colorless product, which was weighed to calculate the yield.
Wherein the compounds Cat-001, cat-002, cat-003 and Cat-004 are the compounds synthesized in examples 1 to 4, and the compound 1 is a commercial comparative catalyst, and the reaction formula is as follows:
the reaction results are shown in Table 1 below:
TABLE 1 comparative test results of Suzuki reaction
From the above, it is clear that the metal compound containing a tri-discoene carbene structure (examples 1 to 4, test numbers 1 to 4) prepared by the method of the present invention has a great influence on the cost control of raw materials, the ease of post-treatment has a great advantage in cost control, which cannot be achieved by the comparative example, because the metal compound containing a tri-discoene carbene structure can stabilize intermediates in the catalytic cycle in the application compared with the comparative example 1 (test number 5), so that the catalytic efficiency is improved, and the Suzuki catalytic reaction can be achieved in a very high yield with only one ten thousandth of the amount. The carbene structure in the molecular structure introduces a tri-dish alkene substituent with large steric hindrance due to the active center, on one hand, the attack on the active center is hindered by the steric protection effect, and on the other hand, the reactivity of the active intermediate is reduced due to the electronic interaction between the tri-dish alkene substituent and the active center, and a very good stability effect is achieved on the active intermediate, so that higher catalytic activity is realized.
Example 6 catalytic comparison of Hartwig-Buchwald coupling reactions
To a Schlenk tube containing a magneton, 1.0mmol of p-methoxybromobenzene, 1.1mmol of potassium t-butoxide and 0.01% mmol of catalyst (compounds Cat-001, cat-002, cat-003, cat-004, 2) were successively added, followed by 1.2mmol of diphenylamine and 1mL of toluene, and stirred at 100℃for 2 hours. Then, after dissolution with dichloromethane, alumina was added and column chromatography (eluent dichloromethane/petroleum ether=2:1) to give a colorless product, which was weighed to calculate the yield.
Wherein the compounds Cat-001, cat-002, cat-003 and Cat-004 are the compounds synthesized in examples 1 to 4, and the compound 2 is a commercial comparative catalyst, and the reaction formula is as follows:
the reaction results are shown in Table 2 below:
table 2, hartwig-Buchwald reaction comparative test results
From the above, it is clear that the metal compound containing a tri-dish alkene carbene structure (examples 1 to 4, test numbers 6 to 9) prepared by the method of the present invention has a great influence on the cost control of raw materials, and the difficulty of post-treatment has a great advantage in cost control, which cannot be achieved in comparative example, because the metal compound containing a tri-dish alkene carbene structure can stabilize intermediates in the catalytic cycle in the application compared with comparative example 2 (test number 10), so that the catalytic efficiency is improved, and the Hartwig-Buchwald catalytic reaction can be achieved in a very high yield with only one ten thousandth of the amount. The carbene structure in the molecular structure introduces a tri-dish alkene substituent with large steric hindrance due to the active center, so that on one hand, the attack on the active center is hindered by the steric protection effect, and on the other hand, the reactivity of the active intermediate is reduced due to the electronic interaction between the tri-dish alkene substituent and the active center, and a very good stability effect is achieved on the active intermediate. Thus achieving a higher catalytic activity.
Example 7Heck coupling reaction catalytic comparison
1.0mmol of p-bromobenzoic acid, 1.2mmol of potassium carbonate and 0.01% mmol of catalyst (compounds Cat-001, cat-002, cat-003, cat-004, 3) were successively added to a Schlenk tube containing a magnet, followed by 1.2mmol of acrylic acid, 1mL of xylene and stirring at 120℃for 2 hours. Then, after dissolution with dichloromethane, alumina was added and column chromatography (eluent dichloromethane/petroleum ether=4:1) to give a colorless product, which was weighed to calculate the yield.
Wherein the compounds Cat-001, cat-002, cat-003 and Cat-004 are the compounds synthesized in examples 1 to 4, and the compound 3 is a commercial comparative catalyst, and the reaction formula is as follows:
the reaction results are shown in Table 3 below:
TABLE 3 Heck reaction comparative test results
From the above, it is clear that the metal compound containing a tri-dish alkene carbene structure (examples 1 to 4, test numbers 11 to 14) prepared by the method of the present invention has a great effect on the cost control of raw materials, the ease of post-treatment has a great advantage in cost control, which cannot be achieved in comparative example, because the metal compound containing a tri-dish alkene carbene structure can stabilize intermediates in the catalytic cycle in the application compared with comparative example 3 (test number 15), so that the catalytic efficiency is improved, heck catalytic reaction can be achieved in a very high yield with only one ten thousandth of the amount of the catalyst used in the industrial production. The carbene structure in the molecular structure introduces a tri-dish alkene substituent with large steric hindrance due to the active center, on one hand, the attack on the active center is hindered by the steric protection effect, and on the other hand, the reactivity of the active intermediate is reduced due to the electronic interaction between the tri-dish alkene substituent and the active center, and a very good stability effect is achieved on the active intermediate, so that higher catalytic activity is realized.
Example 8Still reaction catalytic comparison
To a Schlenk tube containing a magneton, 1.0mmol of p-methoxybromobenzene, 1.2mmol of potassium fluoride and 0.01% mmol of catalyst (compounds Cat-001, cat-002, cat-003, cat-004, 4) were successively added, followed by 1.2mmol of tributylphenyl alkene, 1mL of dioxane, and stirring at 100℃for 6 hours. Then, after dissolution with dichloromethane, alumina was added and column chromatography (eluent dichloromethane/petroleum ether=4:1) to give a colorless product, which was weighed to calculate the yield.
Wherein the compounds Cat-001, cat-002, cat-003 and Cat-004 are the compounds synthesized in examples 1 to 4, and the compound 4 is a commercial comparative catalyst, and the reaction formula is as follows:
the reaction results are shown in Table 4 below:
table 4, results of Still reaction comparative test
From the above, it is clear that the metal compound containing a tri-dish alkene carbene structure (examples 1 to 4, test numbers 16 to 19) prepared by the method of the present invention has a great effect on the ease of post-treatment in the application and a great advantage in the cost control, which cannot be achieved in the comparative example, because the metal compound containing a tri-dish alkene carbene structure can stabilize intermediates in the catalytic cycle, so that the catalytic efficiency is improved, and the stills catalytic reaction can be achieved in a very high yield with only one ten thousandth of the amount, compared with the comparative example 4 (test number 20). The carbene structure in the molecular structure introduces a tri-dish alkene substituent with large steric hindrance due to the active center, on one hand, the attack on the active center is hindered by the steric protection effect, and on the other hand, the reactivity of the active intermediate is reduced due to the electronic interaction between the tri-dish alkene substituent and the active center, and a very good stability effect is achieved on the active intermediate, so that higher catalytic activity is realized.
Example 9Negishi reaction catalytic comparison
To a Schlenk tube containing a magneton, 1.0mmol of p-methoxybromobenzene, 1.2mmol of potassium carbonate and 0.01% mmol of catalyst (compounds Cat-001, cat-002, cat-003, cat-004, 5) were successively added, followed by 1.2mmol of phenylzinc chloride, 1mL of tetrahydrofuran and stirring at 60℃for 6 hours. Then, after dissolution with dichloromethane, alumina was added and column chromatography (eluent dichloromethane/petroleum ether=4:1) to give a colorless product, which was weighed to calculate the yield.
Wherein the compounds Cat-001, cat-002, cat-003 and Cat-004 are the compounds synthesized in examples 1 to 4, and the compound 5 is a commercial comparative catalyst, and the reaction formula is as follows:
the reaction results are shown in Table 5 below:
table 5, negishi reaction comparative test results
From the above, it is clear that the metal compound containing a tri-dish alkene carbene structure (examples 1 to 4, test numbers 21 to 24) prepared by the method of the present invention has a great influence on the cost control of raw materials, and the ease of post-treatment has a great advantage in cost control, which cannot be achieved by the comparative example, because the metal compound containing a tri-dish alkene carbene structure can stabilize intermediates in the catalytic cycle in the application compared with comparative example 5 (test number 25), so that the catalytic efficiency is improved, and the Negishi catalytic reaction can be achieved in a very high yield with only one ten thousandth of the amount. The carbene structure in the molecular structure introduces a tri-dish alkene substituent with large steric hindrance due to the active center, on one hand, the attack on the active center is hindered by the steric protection effect, and on the other hand, the reactivity of the active intermediate is reduced due to the electronic interaction between the tri-dish alkene substituent and the active center, and a very good stability effect is achieved on the active intermediate, so that higher catalytic activity is realized.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Claims (5)
1. A metal compound comprising a tri-discoene carbene structure, characterized in that: the structure is that,
，
including R1, R2, R3, R4, R5, R6, R7, R8, M.
2. A metal compound containing a tri-discoene carbene structure according to claim 1, characterized in that: the R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from any one of-H, -D, -T, -Cl, -F, -CN, -CD3, -CF3, -OCF3, substituted or unsubstituted alkyl group with carbon number of 1-15, substituted or unsubstituted alkoxy group with carbon number of 1-15, linear substituted or unsubstituted olefin group with carbon number of 2-15, substituted or unsubstituted alkyl group with carbon number of 1-15, fluorinated alkoxy group with carbon number of 1-15, linear substituted or unsubstituted alkylene group with carbon number of 2-15, substituted or unsubstituted aryl group with carbon number of 5-20, substituted or unsubstituted heteroaryl group with carbon number of 5-20, substituted or unsubstituted condensed ring aryl group with carbon number of 5-20 or substituted or unsubstituted condensed ring aryl group with carbon number of 5-20.
3. A metal compound containing a tri-discoene carbene structure according to claim 1, characterized in that: m represents Ir or Rh.
4. A metal compound containing a tri-discoene carbene structure according to claim 1, characterized in that: the triptycene carbene allylpalladium compound according to claim 1, wherein the triptycene carbene allylpalladium compound is used in a catalyst for a Suzuki reaction, a Buchwald-Hartwig reaction, a Heck reaction, a Still reaction or a Negishi reaction.
5. The metal compound containing a tri-discoene carbene structure and the application thereof according to claim 1, wherein the metal compound is characterized in that: the use of a metal compound according to claim 1, which contains a tri-discoene carbene structure, in a catalyst.
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