CN116217625A - CNC (computer numerical control) tridentate ruthenium complex as well as preparation method and application thereof - Google Patents
CNC (computer numerical control) tridentate ruthenium complex as well as preparation method and application thereof Download PDFInfo
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- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims description 17
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000007259 addition reaction Methods 0.000 claims abstract description 11
- 238000006197 hydroboration reaction Methods 0.000 claims abstract description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYRLFYTZNXGQIK-UHFFFAOYSA-N 2,6-diethynylpyridine Chemical compound C#CC1=CC=CC(C#C)=N1 VYRLFYTZNXGQIK-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- -1 ether compound Chemical class 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 abstract description 16
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 210000000080 chela (arthropods) Anatomy 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 150000001450 anions Chemical class 0.000 abstract 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 abstract 1
- 159000000000 sodium salts Chemical class 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 240000006915 Petasites Species 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229940002612 prodrug Drugs 0.000 description 1
- 239000000651 prodrug Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
-
- 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
- B01J2531/821—Ruthenium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to the fields of coordination chemistry and metal organic chemistry, and discloses a CNC tridentate ruthenium complex which can be used for catalyzing alkyne hydroboration addition reaction. 2, 6-di (ethynyl) pyridine is used as a raw material, and the CNC type tridentate ruthenium complex is synthesized through two steps: first, 2, 6-di (ethynyl) pyridine (CNC pincer ligand L) is utilized with ruthenium metal source RuCl 2 (PPh 3 ) 3 Reacting to obtain CNC type tridentate ruthenium complex 1 with a negative electron on metal, performing oxidative dehydrogenation on N-chlorosuccinimide to obtain CNC type tridentate ruthenium complex 2 with counter anion of 2 chloride ions, removing excessive NCS and its derivatives, mixing the CNC type tridentate ruthenium complex 2 with sodium salt (NaBPh) 4 ) And (3) reacting to obtain the final CNC tridentate ruthenium complex. CNC type tridentate ruthenium complex can be high in room temperature nitrogen atmosphereEffectively catalyzing the hydroboration addition reaction of phenylacetylene to prepare the anti-Mahalanobis regular addition product: 2.5mol% of CNC tridentate ruthenium complex, phenylacetylene can be converted into the product 4b in 80% yield after 18 hours at room temperature.
Description
Technical Field
The invention relates to the fields of organic chemistry, coordination chemistry and metal organic chemistry, in particular to synthesis, structure, preparation method and application of CNC (computerized numerical control) tridentate ruthenium complex for hydroboration addition reaction of phenylacetylene.
Background
The hydroboration of unsaturated alkynes is a green reaction with 100% atomic economy and can be used to prepare a range of boron containing compounds. However, these boron-containing substrates have important applications in green organic synthetic chemistry, such as for the Suzuki-Miyaura coupling reactions, petasites reactions, etc., which allow for the convenient and efficient construction of several important prodrugs. Thus, the reaction has been the focus of research on green synthetic chemistry (acs. Catalyst. 2021,11, 1-18.).
The hydroboration addition reaction of alkynes and organoboron reagents has problems of chemical selectivity and regioselectivity, and traditionally, the selective one-time addition reaction of alkynes and boranes is an important method for preparing alkenyl boronates, which generally gives mainly anti-mahalanobis regular addition products (j.am.chem.soc.2017, 139, 8130-8133.). Therefore, from the standpoint of green chemistry, it is important to develop new catalysts to catalyze the hydroboration of unsaturated alkynes.
Disclosure of Invention
Metal heterocyclic compounds containing a ruthenium vinylidene bond in the ring have not been reported so far. As a brand new CNC tridentate ruthenium complex containing an in-ring ruthenium vinylidene bond, the complex has good catalytic application prospect. Considering the importance of catalyzing the borohydride addition reaction of alkynes, the inventors of the present invention applied the prepared various CNC-type tridentate ruthenium complexes to the catalytic process with good results.
The invention aims at realizing the following technical scheme:
the invention relates to a CNC tridentate ruthenium complex shown in a formula (I):
2. the preparation method of the CNC tridentate ruthenium complex shown in the formula (I) is characterized by comprising the following synthesis steps:
s1: preparation of CNC tridentate ruthenium complex 1:
under the protection of N2, ruthenium metal source RuCl is added at room temperature 2 (PPh 3 ) 3 、PPh 3 And 2, 6-bis (ethynyl) pyridine (CNC pincer ligand L) in an organic solvent. Stirring to obtain orange solution. Concentrating the reaction solution, adding ether compound for precipitation, filtering, washing the obtained solid by adopting diethyl ether solvent, and vacuum drying the yellow solid 1.
S2: preparation of CNC tridentate ruthenium complex 2:
under the protection of inert gas, a solid mixture of CNC tridentate ruthenium complex 1 and N-chlorosuccinimide NCS is dissolved in an organic solvent at room temperature. Stirring at room temperature gave a tan solution. Concentrating the reaction solution, adding ether compound for precipitation, filtering, washing the solid, and drying in vacuum to obtain yellow solid 2.
S3: preparation of CNC tridentate ruthenium complex:
CNC type tridentate ruthenium complex 2 was dissolved in dichloromethane at room temperature. Dropwise adding the mixture into a methanol solution of sodium tetraphenylborate. Stirring at room temperature produced a yellow solid. After filtration, the resulting solid was washed with diethyl ether and dried by suction to give yellow solid 3.
In some examples of the preparation method of CNC type tridentate ruthenium complex shown in formula (I), ruthenium metal source RuCl 2 (PPh 3 ) 3 、PPh 3 And 2, 6-di (ethynyl) pyridine in a feed molar ratio of 1:1:2。
In some examples of the preparation method of CNC type tridentate ruthenium complex shown in formula (I), the feeding mole ratio of the CNC type tridentate ruthenium complex 1 and NCS in the step S2 is 11:17.
In some embodiments of the preparation method of the CNC type tridentate ruthenium complex shown in the formula (I), the feeding mass ratio of the CNC type tridentate ruthenium complex 2 and the sodium tetraphenylborate in the step S3 is 75:94.
In some embodiments the organic solvent of S1, S2, S3 may be selected to be dichloromethane.
In some embodiments the reaction room temperature of S1, S2, S3 is 5 ℃ to 35 ℃.
In some embodiments the precipitation method of the S2 and S3 steps can be adding diethyl ether for precipitation.
On the other hand, the application of the ruthenium complex shown in the formula (I) in catalyzing the hydroboration addition reaction of phenylacetylene is characterized in that CNC tridentate ruthenium complex shown in the formula (I), phenylacetylene and HBpin are added into a reactor together to react at room temperature to obtain a product alpha-isomer and a product beta-isomer, wherein the reaction formula is as follows:
in some embodiments the feed ratio of the CNC tridentate ruthenium complex according to formula (I) in the reaction is 2.5mol% to 5mol%, particularly preferably 2.5mol%.
In some embodiments, the product β -isomer isolation yield is greater than 80%.
In some embodiments, the beta-isomer reaction product selectivity is greater than 96%.
In some embodiments, the selectivity of the β -isomer reaction product is greater than 98%.
The invention has the following advantages:
(1) Each step of synthesis of the CNC tridentate ruthenium complex is completed under the room temperature condition, the operation is simple and convenient, and the novel process for preparing the compound is provided.
(2) The CNC tridentate ruthenium complex has high catalytic efficiency and small catalyst consumption, and only 2.5mol percent of catalyst is needed for preparing the anti-Mahalanobis regular addition product by catalyzing the hydroboration addition reaction of phenylacetylene.
(3) The catalytic condition is mild, and phenylacetylene can be efficiently converted into a target product 4b at room temperature.
(4) The catalytic reaction is relatively specific, the side reaction is less, and the yield is high.
General synthetic procedure
For the purpose of illustrating the invention, examples are set forth below. It is to be understood that the invention is not limited to these examples but provides a method of practicing the invention.
In general, the compounds of the present invention may be prepared by the methods described herein. The following examples serve to further illustrate the context of the present invention.
Those skilled in the art will recognize that: the chemical reactions described herein may be used to suitably prepare many other compounds of the present invention, and other methods for preparing the compounds of the present invention are considered to be within the scope of the present invention. For example, the synthesis of those non-exemplified compounds according to the invention can be successfully accomplished by modification methods, such as appropriate protection of interfering groups, by use of other known reagents in addition to those described herein, or by some conventional modification of the reaction conditions, by those skilled in the art. In addition, the reactions disclosed herein or known reaction conditions are also well-known to be applicable to the preparation of other compounds of the present invention.
Drawings
FIG. 1 is an X-ray single crystal diffraction structure diagram of CNC tridentate ruthenium complex 1.
FIG. 2 is an X-ray single crystal diffraction structure of CNC tridentate ruthenium complex.
FIG. 3 is a CNC type tridentate ruthenium complex 1 1 H-NMR spectrum.
FIG. 4 is a CNC type tridentate ruthenium complex 1 31 P{ 1 H } NMR spectra.
FIG. 5 is a CNC type tridentate ruthenium complex 1 13 C{ 1 H } NMR spectra.
FIG. 6 is a CNC threeRuthenium complexes 1 H-NMR spectrum.
FIG. 7 is a CNC type tridentate ruthenium complex 31 P{ 1 H } NMR spectra.
FIG. 8 is a CNC type tridentate ruthenium complex 13 C{ 1 H } NMR spectra.
The above spectra were all detected using methods and conditions conventional in the art.
Detailed Description
The following description of the present invention is provided with reference to the accompanying drawings, but is not limited to the following description, and any modifications or equivalent substitutions of the present invention should be included in the scope of the present invention without departing from the spirit and scope of the present invention.
The inventors of the present invention have found that CNC pincer ligand L (40 mg,0.32 mmol) was mixed with metallic ruthenium source RuCl 2 (PPh 3 ) 3 (150 mg,0.16 mmol) and triphenylphosphine (PPh) 3 41mg,0.16 mmol) in dichloromethane (CH 2 Cl 2 5 mL) in a solvent at room temperature, and 80% of separation yield can be obtained after 10 minutes, thus obtaining the CNC tridentate ruthenium complex 1 with a negative electron on the metal. The complex is continuously reacted with N-chlorosuccinimide (NCS, 23mg,0.17 mmol) in CH2Cl2 for 30 minutes at room temperature, and then the complex can be oxidized to form CNC tridentate ruthenium complex 2, and the separation yield can reach 77%. In a methanol solution under a nitrogen atmosphere, the CNC tridentate ruthenium complex 2 can be continuously reacted with NaBPh 4 After reacting at room temperature for 30 minutes, the CNC tridentate ruthenium complex was isolated in 95% yield by filtration. In particular, the reaction equation of the complex containing the ring ruthenium vinylidene bond is shown as a formula I.
Formula I:
preparation of CNC tridentate ruthenium complex 1:
at room temperature, at N 2 Under protection, ruthenium metal source RuCl 2 (PPh 3 ) 3 (150mg,0.16mmol)、PPh 3 A solid mixture of (41 mg,0.16 mmol) and 2, 6-bis (ethynyl) pyridine (40 mg,0.32 mmol) was dissolved in solvent dichloromethane (5 mL). Stirring at room temperature for 10min to obtain orange solution. The reaction solution was concentrated to 3mL, and 30mL of diethyl ether was added to the remaining solution to precipitate a product. After filtration, the resulting solid was washed with diethyl ether (2×30 mL) and dried in vacuo to give yellow solid 1 in 80% yield. The reaction equation is shown in formula III.
Formula III:
the specific nuclear magnetic characterization data of the compound are as follows: 1 H-NMR(600MHz,Chloroform-d,δppm):11.79(d,J P-H ＝28.6Hz,2H,C 1 H/C 9 H),6.68(t,J P-H ＝7.9Hz,1H,C 5 H),6.18(d,J P-H ＝7.9Hz,2H,C 4 H/C 6 H),7.71-6.05(m,63H,other aromatic protons plus C 5 H and C 4 H/C 6 H)； 31 P{ 1 H}NMR(252MHz,Chloroform-d,δppm):37.67(s,CPPh 3 ),8.69(s,RuPPh 3 )； 13 C{ 1 H}NMR(151MHz,Chloroform-d,δppm):264.41(m,C 1 /C 9 ),166.22(d,J P-C ＝38.2Hz,C 3 /C 7 ),129.59(s,C 5 ),120.5(d,J P-C ＝88.4Hz,C 2 /C 8 ),112.87(s,C 4 /C 6 ),135.5-127.6(m,PPh 3 ).
preparation of CNC tridentate ruthenium complex 2:
at room temperature, at N 2 A solid mixture of CNC tridentate ruthenium complex 1 (150 mg,0.11 mmol) and NCS (23 mg,0.17 mmol) was dissolved in solvent dichloromethane (5 mL) under protection. Stirring at room temperature for 30min to obtain a brown yellow solution. The reaction solution was concentrated to 3mL, and 30mL of diethyl ether was added to the remaining solution to precipitate a product. After filtration, the resulting solid was washed with diethyl ether (2×30 mL) and dried in vacuo to give yellow solid 2 in 77% yield. The reaction equation is shown in formula IV.
Formula IV:
preparation of CNC tridentate ruthenium complex:
CNC type tridentate ruthenium complex 2 (150 mg,0.11 mmol) in dichloromethane (3 mL) was added at room temperature. Drop into methanol solution of sodium tetraphenylborate (188 mg/20mL CH) 3 OH). After the completion of the dropwise addition, the mixture was stirred at room temperature for 0.5 hour in air to give a yellow solid. After filtration, the resulting solid was washed with diethyl ether (3×10 mL) and dried to give yellow solid 3 in 95% yield. The reaction equation is shown in formula V.
Formula V:
the specific nuclear magnetic characterization data of the compound are as follows: 1 H-NMR(600MHz,Dichloromethane-d2,δppm):11.09(d,J P-H ＝19.7Hz,1H,C 9 H),6.74(t,J P-H ＝7.9Hz,1H,C 5 H),6.03(d,J P-H ＝7.9Hz,1H,C 4 H),5.83(d,J P-H ＝7.9Hz,1H,C 6 H),7.72-6.22(m,101H,other aromatic protons plus C 5 H)； 31 P{ 1 H}NMR(252MHz,Dichloromethane-d2,δppm):11.67(s,CPPh 3 ),3.43(s,CPPh 3 ),28.60(s,RuPPh 3 )； 13 C{ 1 H}NMR(151MHz,Dichloromethane-d2,δppm):366.50(s,C 1 ),237.62(s,C 9 ),163.36(d,J P-C ＝27.6Hz,C 7 ),160.37(d,J P-C ＝20.6Hz,C 3 ),142.20(s,C 5 ),117.18(s,C 6 ),117.00(s,C 4 ),116.58(d,J P-C ＝80.5Hz,C 2 ),98.87(d,J P-C ＝110.2Hz,C 8 ),141.2-116.3(m,other aromatic carbons).
preparing 4b by catalyzing hydroboration addition reaction of phenylacetylene with CNC tridentate ruthenium complex:
in a glove box filled with nitrogen, CNC tridentate ruthenium complex (9.76 mg,2.5 mol%), DCM (1.0 mL), HBpin (30.7 mg,0.24 mmol) and phenylacetylene (22 μl,0.2 mmol) were added sequentially in a 4mL glass bottle. The reaction mixture was allowed to stir at room temperature for 16 hours, then the reaction solution was exposed to air, DCM (2 mL) was added, the reaction quenched, and the solvent was removed under reduced pressure. The reaction mixture was first subjected to 1H-NMR monitoring reaction analysis to determine the selectivity to the desired alkenyl borate. The separated mixture was then evaporated under reduced pressure, the product was separated by silica gel column chromatography (200-300 mesh), ethyl acetate/hexane was purified as eluent to give the product and the 4b yield was calculated.
After successfully obtaining CNC tridentate ruthenium complex, the inventors of the present invention found that it was under a nitrogen atmosphere in CH 2 Cl 2 The anti-Mahalanobis regular addition product 4b can be prepared by catalyzing the hydroboration addition reaction of phenylacetylene in a solvent under the condition of room temperature. Under the nitrogen atmosphere, the reaction time is limited to 18 hours, the reaction temperature is limited to room temperature, the equivalent of the catalyst is limited to 5.0mol%, the raw material phenylacetylene can be converted into beta-alkenyl borate with high selectivity, and the separation yield of the target product 4b reaches 80%. If the catalyst CNC type tridentate ruthenium complex is changed into CNC type tridentate ruthenium complex 1 and PPh 3 CH 3 Only trace amounts of product were observed on the Br, indicating that the CNC tridentate ruthenium complex did catalyze the reaction. If the equivalent weight of the catalyst CNC type tridentate ruthenium complex is reduced to 2.5mol%, the selectivity and the yield of the reaction are unchanged, and the catalyst is changed into N 2 In the atmosphere, the catalyst amount was reduced to 1.0mol%, the selectivity of the reaction was unchanged, but the yield was greatly reduced. This indicates that the optimum equivalent weight of the reaction catalyst is 2.5mol%.
The catalytic reaction equation is shown in formula II.
Formula II:
the invention aims at realizing the following technical scheme:
in a glove box filled with nitrogen atmosphere, CNC tridentate ruthenium complex (9.76 mg,2.5 mol%) and DCM (1.0 mL) were added first, HBpin (30.7 mg,0.24 mmol) and alkyne ((22. Mu.l, 0.2 mmol)) were then injected into a 4mL glass bottle, the reaction mixture was allowed to stir at room temperature for 16 hours, then the reaction solution was exposed to air, DCM (2 mL) was added to quench the reaction, and the solvent was removed under reduced pressure, the reaction mixture was first subjected to 1 H-NMR monitors the reaction analysis to determine the selectivity of the desired alkenyl borate. The separated mixture was then evaporated under reduced pressure, the product was separated by silica gel column chromatography (200 to 300 mesh), and ethyl acetate/hexane was purified as an eluent to give the product and the yield was calculated.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
Claims (10)
1. A CNC type tridentate ruthenium complex represented by formula (I):
2. the preparation method of the CNC tridentate ruthenium complex shown in the formula (I) is characterized by comprising the following synthesis steps:
s1: (1) synthesis of CNC type tridentate ruthenium complex 1:
under the condition of inert gas at room temperature, ruthenium metal source RuCl is prepared 2 (PPh 3 ) 3 、PPh 3 And 2, 6-bis (ethynyl) pyridine in an organic solvent, and further adding HBF thereto 4 ·H 2 O solution, stirringAfter the reaction is completed, adding ether compound to precipitate, separating and washing to obtain CNC tridentate ruthenium complex 1,
s2: (1) synthesis of CNC type tridentate ruthenium complex 2:
under the condition of room temperature and inert atmosphere, dissolving the CNC tridentate ruthenium complex 1 and NCS in an organic solvent, stirring, concentrating a reaction solution, precipitating an ether compound, filtering, drying and washing to obtain the CNC tridentate ruthenium complex 2,
s3: synthesis of the compound of formula (1):
under the condition of room temperature, dropwise adding the CNC tridentate ruthenium complex 2 into an alcohol solution of sodium tetraphenylborate, stirring after the dropwise adding is finished to generate a solid, filtering, washing the obtained solid with an ether compound, and drying to obtain the CNC tridentate ruthenium complex.
3. The process for preparing a CNC tridentate ruthenium complex according to claim 2, wherein the step S2 ruthenium metal source RuCl is 2 (PPh 3 ) 3 And PPh 3 The molar ratio of the feed is 1:0.8 to 1:1.2, preferably 1:1, and the ruthenium metal source RuCl 2 (PPh 3 ) 3 And 2, 6-bis (ethynyl) pyridine in a molar ratio of 1:1 to 1:3, preferably 1:2.
4. The process for preparing a CNC-type tridentate ruthenium complex according to claim 2, wherein the molar ratio of the CNC-type tridentate ruthenium complex 1 to NCS in step S2 is from 11:15 to 11:21, preferably 11:17.
5. The preparation method of the CNC type tridentate ruthenium complex shown in the formula (I) according to claim 2, wherein the feeding mass ratio of the CNC type tridentate ruthenium complex 2 and the sodium tetraphenylborate in the step S3 is 75:87-75:97, preferably 75:94.
6. A preparation method of a CNC type tridentate ruthenium complex shown in a formula (I) is characterized in that room temperature in steps S1, S2 and S3 is 5-35 ℃.
7. The method for preparing a CNC-type tridentate ruthenium complex according to claim 2, wherein the ether compound in the steps S1, S2, S3 is diethyl ether.
8. The application of the ruthenium complex shown in the formula (I) in catalyzing the hydroboration addition reaction of phenylacetylene, which is disclosed in claim 1, is characterized in that CNC tridentate ruthenium complex shown in the formula (I), phenylacetylene and HBpin are added into a reactor together, and react under the condition of room temperature to obtain a product alpha-isomer and a product beta-isomer, wherein the reaction formula is as follows:
9. use according to claim 8, characterized in that the feed ratio of the CNC-type tridentate ruthenium complex is 2.5mol% to 5mol%, preferably 2.5mol%.
10. The use according to claim 8, characterized in that the reaction product β -isomer yield is greater than 80% and the borohydride product β -isomer selectivity is greater than 96%.
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