CN113735896A - Method for preparing Z-configuration-1, 2-di-tin substituted olefin by adopting monoatomic palladium-phosphine ligand - Google Patents
Method for preparing Z-configuration-1, 2-di-tin substituted olefin by adopting monoatomic palladium-phosphine ligand Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 27
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 23
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 150000001345 alkine derivatives Chemical group 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000007259 addition reaction Methods 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 238000010898 silica gel chromatography Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 2
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- OGQGYEMWHUFMQJ-UHFFFAOYSA-N tris(5-ethenyl-2-methoxyphenyl)phosphane Chemical compound COC(C=CC(C=C)=C1)=C1P(C(C=C(C=C)C=C1)=C1OC)C(C=C(C=C)C=C1)=C1OC OGQGYEMWHUFMQJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 150000004678 hydrides Chemical class 0.000 abstract description 3
- -1 stannate hydride Chemical class 0.000 description 17
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229940071182 stannate Drugs 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- CRWVOXFUXPYTRK-UHFFFAOYSA-N pent-4-yn-1-ol Chemical compound OCCCC#C CRWVOXFUXPYTRK-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 description 1
- 239000005498 Clodinafop Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YUIKUTLBPMDDNQ-MRVPVSSYSA-N clodinafop Chemical compound C1=CC(O[C@H](C)C(O)=O)=CC=C1OC1=NC=C(Cl)C=C1F YUIKUTLBPMDDNQ-MRVPVSSYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- REDSKZBUUUQMSK-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC.CCCC[Sn](CCCC)CCCC REDSKZBUUUQMSK-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
- B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- 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
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- 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
- B01J2531/824—Palladium
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Abstract
The invention discloses a method for preparing Z-configuration-1, 2-di-tin substituted olefin by adopting monoatomic palladium-phosphine ligand, which comprises the following steps: 1) preparation of monatomic palladium phosphine ligand porous polymer catalyst Pd1@ POL-1; 2) double stannation addition reaction preparation by adopting single atom palladium phosphine ligand porous polymer to catalyze terminal alkyneZ-1, 2-distannyl substituted alkene product of configuration. The method has low cost and high selectivity, can realize double stannation reaction of high regioselectivity and chemoselectivity of alkyl stannic hydride and terminal alkyne under the heterogeneous condition, and obtains a single configuration, namelyZ-1, 2-distannyl substituted alkene product of configuration.
Description
Technical Field
The invention relates to chemical synthesis, in particular to a method for preparing Z-configuration-1, 2-di-tin substituted olefin by adopting a single-atom palladium-phosphine ligand.
Background
1, 2-distannyl substituted olefins are important synthetic blocks in organic synthesis, (Alois F ü rstner, Marc Heinrich, John J. Murphy, Aurelien Letort, Jakub Flasz, and Petra Philips. Angew. Chem. int. Ed.2018,57, 13575-. The double stannation reaction of alkyne is the only way to construct Z-type-1, 2-di-stannum substituted alkene. How to synthesize 1, 2-di-tin substituted olefins with high selectivity is a challenging task. According to literature reports, Lautens et al (John Mancuso and Mark Lautens. org. Lett.2003,5, 1653-one 1655) used hexaalkylditin as a stannating agent to synthesize a bisstannic compound by catalyzing a terminal alkyne with a palladium/isonitrile complex to achieve a bisstannic product in 2003: the selectivity of tin hydrogen product is 1.5:1, the reaction uses expensive hexabutylditin as a reaction raw material, the reaction range of a substrate is narrow, and the selectivity is insufficient. Most of the existing alkyne di-stannation reactions use alkyl di-tin as a tin source, and the reactions inevitably have the defects of high metal loading, low yield, poor selectivity, insufficient substrate adaptability and the like, and are not favorable for the effective preparation of di-stannation products.
The subsequent group of Kazmaier topics in Germany (Sascha Braune and Uli Kazmaier. Angew. chem. int. Ed.2003,42, 306-. In general, the double stannation reaction using alkyl stannate as a substrate is unfavorable under homogeneous conditions, and forms stannate hydride products easily (Lautens, M., and Mancuso, J.Org.Lett.,2000,2, 671-673).
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing Z-configuration-1, 2-di-tin substituted olefin by adopting a single-atom palladium phosphine ligand. The method has low cost and high selectivity, and can realize double stannation reaction of alkyl stannic hydride and terminal alkyne with high regioselectivity and chemoselectivity under the heterogeneous condition to obtain a single-configuration 1, 2-di-tin substituted alkene product, namely Z-configuration.
The technical scheme for realizing the purpose of the invention is as follows:
the method for preparing the Z-configuration-1, 2-di-tin substituted olefin by adopting the monoatomic palladium-phosphine ligand is different from the prior art in that the method comprises the following steps:
1) preparation of monatomic palladium phosphine ligand porous polymer catalyst Pd1@ POL-1: the phosphine ligand unit and the transition metal salt form a monoatomic dispersed metal/ligand catalytic system under the homogeneous condition by adopting a solvothermal method, and finally, the monoatomic palladium-phosphine ligand porous polymer catalyst Pd is obtained by self-polymerization1@POL-1；
2) A single-atom palladium phosphine ligand porous polymer is adopted to catalyze the double stannation addition reaction of terminal alkyne to prepare a Z-configuration 1, 2-di-tin substituted alkene product.
The monatomic palladium-phosphine ligand porous polymer catalyst Pd in the step 1)1The synthesis general formula of @ POL-1 is:
the single atom palladium phosphine ligand porous polymer catalyst Pd1The preparation process of @ POL-1 is as follows: s1, tris (2-methoxy-5-vinylphenyl) phosphine of the formula (100 mg) and bis triphenylphosphine palladium dichloride of 12mg were dissolved in 5mL of chloroform and stirred at room temperature for 3 hours, followed by addition of 2,2' -azobis (2-methylpropanenitrile) (AIBN, 10mg), the mixture was transferred to an 80 ℃ autoclave for 24 hours and the tetrahydrofuran was removed by suction filtration to obtain Pd as a white solid1@POL-1。
The general formula of the double stannation addition reaction for catalyzing the terminal alkyne in the step 2) is as follows:
the double stannation addition reaction of the catalytic terminal alkyneThe process is as follows: under nitrogen atmosphere, 15.5mg of Pd1@ POL-1 is added into a dry reaction tube with a branch port, the reaction tube is sealed by a rubber diaphragm, 2mL of distilled tetrahydrofuran is added, 1 equivalent of alkyne is added subsequently, 1 equivalent of tributyltin hydride is added into the reaction tube dropwise, the reaction mixture is stirred for 16 hours at room temperature, TLC is used for monitoring until the reaction is completed, the solution is filtered, ethyl acetate is used for washing and suction filtration, the crude product is directly purified by silica gel column chromatography, and petroleum ether, ethyl acetate and 1% triethylamine are used for eluting to obtain the corresponding Z-configuration bistin substituted olefin product.
The technical scheme adopts a single atom palladium phosphine ligand porous polymer as a catalyst, and realizes double stannation reaction of high regioselectivity and chemical selectivity of alkyl stannate hydrogen and terminal alkyne under the heterogeneous condition to obtain a 1, 2-di-tin substituted alkene product with a single configuration (Z-type).
According to the technical scheme, the low-price tributyltin hydride is used as a tin source, so that the reaction cost is reduced; the reaction utilizes the enrichment function of polymer pore channels, and is favorable for improving the activity and the selectivity of the reaction; the reaction catalyst adopts a single atom palladium metallized phosphine ligand porous polymer, which is beneficial to preventing the agglomeration of metal particles, not only can be recycled, but also further improves the chemical selectivity of the reaction and promotes the generation of Z-type-1, 2-distan substituted olefin products.
The method has low cost and high selectivity, and can realize double stannation reaction of alkyl stannic hydride and terminal alkyne with high regioselectivity and chemoselectivity under the heterogeneous condition to obtain a single-configuration 1, 2-di-tin substituted alkene product, namely Z-configuration.
Drawings
FIG. 1 is a hydrogen spectrum of (Z) -5, 6-bis (tributylstannyl) hex-5-en-1-ol in example;
FIG. 2 is a carbon spectrum of (Z) -5, 6-bis (tributylstannyl) hex-5-en-1-ol in example;
FIG. 3 is a hydrogen spectrum of (Z) -1- (2, 3-bis (tributylstannyl) allyl) -1H-indole in example;
FIG. 4 is a carbon spectrum of (Z) -1- (2, 3-bis (tributylstannyl) allyl) -1H-indole in example;
FIG. 5 is a hydrogen spectrum of (Z) - (1- (4-nitrophenyl) ethylene-1, 2-diyl) bis (tributylstannane) in example;
FIG. 6 is a carbon spectrum of (Z) - (1- (4-nitrophenyl) ethylene-1, 2-diyl) bis (tributylstannane) in example;
FIG. 7 is a hydrogen spectrum of (Z) -2, 3-bis (tributylstannyl) allyl (R) -2- (4- ((5-chloro-3-fluoropyridin-2-yl) oxy) phenoxy) propionate in example;
FIG. 8 is a carbon spectrum of (Z) -2, 3-bis (tributylstannyl) allyl (R) -2- (4- ((5-chloro-3-fluoropyridin-2-yl) oxy) phenoxy) propionate in example.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, but the present invention is not limited thereto.
Example 1:
taking 4-pentyn-1-ol as an example, the double stannation reaction is carried out to generate (Z) -5, 6-bis (tributylstannyl) hex-5-en-1-ol, and the reaction equation is as follows:
the preparation method comprises the following specific steps:
(a) the general formula of the catalyst synthesis is as follows:
(b) under nitrogen atmosphere, 15.5mg of Pd1@ POL-1 was added to a dry reaction tube with a mouth, the vial was sealed with a rubber septum and 2mL of distilled tetrahydrofuran was added, followed by 0.5mmol of 4-pentyn-1-ol, then 0.5mmol of tributyltin hydride was added dropwise to the reaction vial, the reaction mixture was stirred at room temperature for 16 hours, monitored by TLC until the reaction was complete, the solution was filtered, washed with ethyl acetate, filtered, and the crude product was purified directly by silica gel column chromatography using petroleum ether, ethyl acetate andeluting with 1% triethylamine to obtain (Z) -5, 6-bis (tributylstannyl) hex-5-en-1-ol with a yield of 72% and a selectivity of 50: 1.
Example 2:
taking 1- (2-propyne) -1H-indole as an example, the di-stannation reaction is carried out to generate (Z) -1- (2, 3-bis (tributylstannyl) allyl) -1H-indole, and the reaction equation is as follows:
the preparation method comprises the following specific steps:
(a) the general formula of the catalyst synthesis is the same as that of example 1;
(b) under nitrogen atmosphere, 15.5mg of Pd1@ POL-1 was added to a dry reaction tube with a branch, the vial was sealed with a rubber septum and 2mL of distilled tetrahydrofuran was added, followed by addition of 0.5mmol of 1- (2-propyne) -1H-indole, then 0.5mmol of tributyltin hydride was added dropwise to the reaction flask, the reaction mixture was stirred at room temperature for 16 hours, monitored by TLC until the reaction was completed, the solution was filtered, washed with ethyl acetate, filtered with suction, and the crude product was directly purified by silica gel column chromatography, eluted with petroleum ether, ethyl acetate and 1% triethylamine to give (Z) -1- (2, 3-bis (tributylstannyl) allyl) -1H-indole in 89% yield with total selectivity c: d ═ 100: 1.
Example 3:
taking p-nitroacetophenone as an example, a bisstannation reaction to form (Z) - (1- (4-nitrophenyl) ethylene-1, 2-diyl) bis (tributylstannane) takes place, the reaction equation is as follows:
the preparation method comprises the following specific steps:
(a) the general formula of the catalyst synthesis is the same as that of example 1;
(b) under nitrogen atmosphere, 15.5mg of Pd1@ POL-1 was added to a dry reaction tube with a port, the vial was sealed with a rubber septum, and added2mL of distilled tetrahydrofuran was added followed by 0.5mmol of p-nitroacetylene, then 0.5mmol of tributyltin hydride was added dropwise to the reaction flask, the reaction mixture was stirred at room temperature for 16 hours, monitored by TLC until the reaction was complete, the solution was filtered, washed with ethyl acetate, filtered, and the crude product was purified directly by silica gel column chromatography, eluting with petroleum ether, ethyl acetate and 1% triethylamine to give (Z) - (1- (4-nitrophenyl) ethylene-1, 2-diyl) bis (tributylstannane) in 67% yield with a selectivity e: f ═ 100: 1.
Example 4:
taking p-clodinafop-propargyl as an example, a bisstannation reaction occurs to produce (Z) -2, 3-bis (tributylstannyl) allyl (R) -2- (4- ((5-chloro-3-fluoropyridin-2-yl) oxy) phenoxy) propionate, the reaction equation is as follows:
the preparation method comprises the following specific steps:
(a) the general formula of the catalyst synthesis is the same as that of example 1;
(b) under nitrogen atmosphere, 15.5mg of Pd1@ POL-1 was added to a dry reaction tube with a branch, the vial was sealed with a rubber septum, and 2mL of distilled tetrahydrofuran was added, followed by addition of 0.5mmol of clodinafop acid, then 0.5mmol of tributyltin hydride was added dropwise to the reaction vial, the reaction mixture was stirred at room temperature for 16 hours, monitored by TLC until the reaction was completed, the solution was filtered, washed with ethyl acetate, suction filtered, and the crude product was directly purified by silica gel column chromatography, eluted with petroleum ether, ethyl acetate, and 1% triethylamine to give (Z) -2, 3-bis (tributylstannyl) allyl (R) -2- (4- ((5-chloro-3-fluoropyridin-2-yl) oxy) propionate in 83% yield with g: h ═ 50:1 selectivity.
As shown in FIGS. 1-8, the NMR and MS data for several of the Z-configuration 1, 2-distannyl substituted olefin products are as follows:
(Z) -5, 6-bis (tributylstannyl) hex-5-en-1-ol:
1H NMR(400MHz,CDCl3)δ＝6.58(1H,s,J＝185.9Hz,76.3Hz),3.67-3.61(2H,m),2.32(2H,t,J＝7.4Hz),1.55-1.41(16H,m),1.36-1.27(13H,m),0.94-0.85(30H,m).13C NMR(100MHz,CDCl3)δ＝167.9,142.1,62.9,47.5,32.3,29.3,29.2,27.5,27.4,25.9,13.7,13.6,10.6,10.6.HRMS(m/z)(ESI):calcd for C29H65OSn2[M+H]+679.3068,found 679.3089；
(Z) -1- (2, 3-bis (tributylstannyl) allyl) -1H-indole:
1H NMR(400MHz,CDCl3)δ＝7.52(1H,d,J＝7.8Hz),7.15(1H,d,J＝8.2Hz),7.08-7.03(1H,m),7.01-6.95(1H,m),6.93(1H,d,J＝3.1Hz),6.46(1H,s,J＝168.4Hz,65.5Hz),6.40(1H,d,J＝3.1Hz),4.78(2H,d,J＝1.3Hz),1.40-1.25(12H,m),1.22-1.14(12H,m),0.88-0.72(30H,m).13C NMR(400MHz,CDCl3)δ＝160.6,144.4,136.4,128.8,128.0,121.2,120.7,119.2,110.1,101.0,60.1,29.2,29.1,27.4,27.3,13.7,13.6,10.8,10.2.HRMS(m/z)(ESI):calcd for C35H63KNSn2[M+K]+774.2630,found 774.2654；
(Z) - (1- (4-nitrophenyl) ethylene-1, 2-diyl) bis (tributylstannane):
1H NMR(400MHz,CDCl3)δ＝8.13(2H,d,J＝8.5Hz),7.09(2H,d,J＝8.6Hz),6.98(1H,s,J＝160.9Hz,66.7Hz),1.56-1.49(5H,m),1.43-1.24(19H,m),1.02-0.98(5H,m),0.94-0.83(25H,m).13C NMR(100MHz,CDCl3)δ＝167.0,158.7,151.7,145.6,126.5,123.5,29.1,29.0,27.3,27.3,13.6,13.6,11.3,11.0.HRMS(m/z)(ESI):calcd for C32H60NO2Sn2[M+H]+728.2657,found 728.2656；
(Z) -2, 3-bis (tributylstannyl) allyl (R) -2- (4- ((5-chloro-3-fluoropyridin-2-yl) oxy) phenoxy) propionate:
1H NMR(400MHz,CDCl3)δ＝7.86(1H,d,J＝2.2Hz),7.47(1H,dd,J＝9.1Hz,2.2Hz),7.09-7.05(2H,m),6.95-6.90(3H,m),4.81-4.72(3H,m),1.65(3H,d,J＝6.8Hz),1.54-1.47(11H,m),1.37-1.29(13H,m),0.98-0.88(30H,m).13C NMR(100MHz,CDCl3)δ＝171.5,159.1,154.9,151.4,148.3,146.9,145.6,145.0,140.1,140.1,124.8,122.2,116.1,75.6,73.2,29.2,29.1,29.0,27.5,27.3,18.7,13.6,10.7,10.4.HRMS(m/z)(ESI):calcd for C41H67ClFNNaO4Sn2[M+Na]+952.2673,found 952.2689.
the method has low cost and high selectivity, and the ratio of the double stannated product to the tin hydrogenated product is as high as more than 100:1 and is far higher than the reported value of the current literature.
Claims (3)
1. The method for preparing Z-configuration-1, 2-di-tin substituted olefin by adopting monoatomic palladium-phosphine ligand is characterized by comprising the following steps:
1) preparation of monatomic palladium phosphine ligand porous polymer catalyst Pd1@ POL-1: the phosphine ligand unit and the transition metal salt form a monoatomic dispersed metal/ligand catalytic system under the homogeneous condition by adopting a solvothermal method, and finally, the monoatomic palladium-phosphine ligand porous polymer catalyst Pd is obtained by self-polymerization1@POL-1；
2) A single-atom palladium phosphine ligand porous polymer is adopted to catalyze the double stannation addition reaction of terminal alkyne to prepare a Z-configuration 1, 2-di-tin substituted alkene product.
2. The method of claim 1 using monatomic palladium phosphineThe method for preparing Z-configuration-1, 2-di-tin substituted olefin by ligand is characterized in that the monoatomic palladium-phosphine ligand porous polymer catalyst Pd in the step 1)1The synthesis general formula of @ POL-1 is:
the single atom palladium phosphine ligand porous polymer catalyst Pd1The preparation process of @ POL-1 is as follows: s1, tris (2-methoxy-5-vinylphenyl) phosphine of the formula (100 mg) and bis triphenylphosphine palladium dichloride of 12mg were dissolved in 5mL of chloroform and stirred at room temperature for 3 hours, followed by addition of 2,2' -azobis (2-methylpropanenitrile) (AIBN, 10mg), the mixture was transferred to an 80 ℃ autoclave for 24 hours and the tetrahydrofuran was removed by suction filtration to obtain Pd as a white solid1@POL-1。
3. The method for preparing 1, 2-di-tin substituted alkenes in Z-configuration using monoatomic palladium phosphine ligands, according to claim 1, wherein the general formula of the double stannation addition reaction of the catalytic terminal alkyne in step 2) is:
the process of the double stannation addition reaction of the catalytic terminal alkyne is as follows: under nitrogen atmosphere, 15.5mg of Pd1@ POL-1 is added into a dry reaction tube with a branch port, the reaction tube is sealed by a rubber diaphragm, 2mL of distilled tetrahydrofuran is added, 1 equivalent of alkyne is added subsequently, 1 equivalent of tributyltin hydride is added into the reaction tube dropwise, the reaction mixture is stirred for 16 hours at room temperature, TLC is used for monitoring until the reaction is completed, the solution is filtered, ethyl acetate is used for washing and suction filtration, the crude product is directly purified by silica gel column chromatography, and petroleum ether, ethyl acetate and 1% triethylamine are used for eluting to obtain the corresponding Z-configuration bistin substituted olefin product.
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| US6124462A (en) * | 1999-11-30 | 2000-09-26 | E. I. Du Pont De Nemours And Company | Catalysis using phosphine oxide compounds |
| US20050176987A1 (en) * | 2001-03-09 | 2005-08-11 | Lukas Goossen | Method for producing vinyl, aryl and heteroaryl acetic acids and derivatives thereof |
| WO2011156921A2 (en) * | 2010-06-14 | 2011-12-22 | Gino Georges Lavoie | Catalyst ligands, catalytic ligand complexes and polymerization processes using same |
| CN110753680A (en) * | 2017-06-20 | 2020-02-04 | 大金工业株式会社 | Method for producing butadiene compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6124462A (en) * | 1999-11-30 | 2000-09-26 | E. I. Du Pont De Nemours And Company | Catalysis using phosphine oxide compounds |
| US20050176987A1 (en) * | 2001-03-09 | 2005-08-11 | Lukas Goossen | Method for producing vinyl, aryl and heteroaryl acetic acids and derivatives thereof |
| WO2011156921A2 (en) * | 2010-06-14 | 2011-12-22 | Gino Georges Lavoie | Catalyst ligands, catalytic ligand complexes and polymerization processes using same |
| CN110753680A (en) * | 2017-06-20 | 2020-02-04 | 大金工业株式会社 | Method for producing butadiene compound |
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| CN114853804A (en) * | 2022-04-29 | 2022-08-05 | 浙江大学 | Method for synthesizing high-regioselectivity alpha-alkenyl stannane by hydrogenation of terminal alkyne martensitic tin |
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