CN113735896B - Method for preparing Z-configuration-1, 2-ditin substituted olefin by adopting monoatomic palladium phosphine ligand - Google Patents
Method for preparing Z-configuration-1, 2-ditin substituted olefin by adopting monoatomic palladium phosphine ligand Download PDFInfo
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- CN113735896B CN113735896B CN202010459158.0A CN202010459158A CN113735896B CN 113735896 B CN113735896 B CN 113735896B CN 202010459158 A CN202010459158 A CN 202010459158A CN 113735896 B CN113735896 B CN 113735896B
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 26
- 239000003446 ligand Substances 0.000 title claims abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 21
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000007259 addition reaction Methods 0.000 claims abstract description 7
- 125000002355 alkine group Chemical group 0.000 claims abstract 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 16
- 150000001345 alkine derivatives Chemical class 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 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
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 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 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 5
- 229940071182 stannate Drugs 0.000 abstract description 4
- -1 alkyl hydrogen Chemical compound 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 5
- 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
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- GAZZTEJDUGESGQ-UHFFFAOYSA-N 1-ethynyl-4-nitrobenzene Chemical group [O-][N+](=O)C1=CC=C(C#C)C=C1 GAZZTEJDUGESGQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- CRWVOXFUXPYTRK-UHFFFAOYSA-N pent-4-yn-1-ol Chemical compound OCCCC#C CRWVOXFUXPYTRK-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JBDHZKLJNAIJNC-LLVKDONJSA-N clodinafop-propargyl Chemical group C1=CC(O[C@H](C)C(=O)OCC#C)=CC=C1OC1=NC=C(Cl)C=C1F JBDHZKLJNAIJNC-LLVKDONJSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 229910001134 stannide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
- 229910052721 tungsten Inorganic materials 0.000 description 1
- UDKYUQZDRMRDOR-UHFFFAOYSA-N tungsten Chemical compound [W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W] UDKYUQZDRMRDOR-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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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
- 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
-
- 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
-
- 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
- B01J31/24—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
-
- 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
- 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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- 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
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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
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing Z-configuration-1, 2-stannous substituted olefin by adopting monoatomic palladium phosphine ligand, which comprises the following steps: 1) Preparing a monoatomic palladium phosphine ligand porous polymer catalyst Pd 1 @POL-1; 2) The 1, 2-ditin substituted olefin product with Z-configuration is prepared by adopting a diatomic palladium phosphine ligand porous polymer to catalyze the double tin addition reaction of terminal alkyne. The method has low cost and high selectivity, and can realize double-stannation reaction of high regioselectivity and chemical selectivity of alkyl hydrogen stannate and terminal alkyne under heterogeneous condition to obtain 1, 2-ditin substituted olefin product with single configuration, namely Z-configuration.
Description
Technical Field
The invention relates to chemical synthesis, in particular to a method for preparing Z-configuration-1, 2-stannous substituted olefin by adopting monoatomic palladium phosphine ligand.
Background
1, 2-Ditin substituted olefins are important synthetic blocks ,(Alois Fürstner,Marc Heinrich,John J.Murphy,Aurelien Letort,Jakub Flasz,and Petra Philipps.Angew.Chem.Int.Ed.2018,57,13575-13581.), in organic synthesis that can be readily converted to olefins of various functional groups by Migita-Kosugi-Stille cross-coupling reactions (Mitchell, t.n. (2004). A.de Meijere and f.diederich, wiley-VCH, weinheim, 125-16.). Double tin reaction of alkyne is the only way to construct Z-type-1, 2-ditin substituted alkene. How to synthesize 1, 2-ditin 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, 1653-1655) used hexaalkylditin as a stannating agent to effect a ditin product by catalyzing the synthesis of a ditin compound from a terminal alkyne by a palladium/isonitrile complex: tin hydrogen product=1.5:1 selectivity, the expensive hexabutylditin is used as a reaction raw material in the reaction, the reaction range of the substrate is narrow, and the selectivity is insufficient. Most of the existing alkyne double-tin reactions use alkyl ditin as a tin source, and the reactions inevitably have the defects of high metal load, low yield, poor selectivity, insufficient substrate adaptability and the like, so that the preparation of double-tin products is unfavorable.
Then, the Kazmaier subject group (Sascha Braune and Uli kazmaier. Angel. Chem. Int. Ed.2003,42, 306-308) in germany uses a carbonyl complex coordinated by molybdenum/tungsten as a catalytic carrier to realize the double tin reaction with high selectivity of alkyne, but unfortunately, the method only can realize the effective conversion of 6 alkynes, the yield is not high, and the high-efficiency conversion of most alkyne Z-type-1, 2-ditin substituted alkene cannot be realized. In general, double tin reactions with alkyl hydrogen stannides as substrates are disadvantageous under homogeneous conditions, and tin hydrogenation products (Lautens, m., and Mancuso, j.org. lett.,2000,2,671-673) are readily formed.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a method for preparing Z-configuration-1, 2-stannous substituted olefin by adopting monoatomic palladium phosphine ligand. The method has low cost and high selectivity, and can realize double-stannation reaction of high regioselectivity and chemical selectivity of alkyl hydrogen stannate and terminal alkyne under heterogeneous condition to obtain 1, 2-ditin substituted olefin product with single configuration, namely Z-configuration.
The technical scheme for realizing the aim of the invention is as follows:
the method for preparing Z-configuration-1, 2-ditin substituted olefin by adopting monoatomic palladium phosphine ligand is different from the prior art in that the method comprises the following steps:
1) Preparation of a monatomic palladium phosphine ligand porous Polymer catalyst Pd 1 @ POL-1: adopting a solvothermal method to enable phosphine ligand units and transition metal salts to form a monoatomic dispersed metal/ligand catalytic system under a homogeneous condition, and finally obtaining a monoatomic palladium phosphine ligand porous polymer catalyst Pd 1 @POL-1 through self polymerization;
2) The 1, 2-ditin substituted olefin product with Z-configuration is prepared by adopting a diatomic palladium phosphine ligand porous polymer to catalyze the double tin addition reaction of terminal alkyne.
The synthesis general formula of the monoatomic palladium phosphine ligand porous polymer catalyst Pd 1 @POL-1 in the step 1) is as follows:
The preparation process of the monoatomic palladium phosphine ligand porous polymer catalyst Pd 1 @POL-1 comprises the following steps: 100mg of S1 in the general formula, i.e., tris (2-methoxy-5-vinylphenyl) phosphine and 12mg of ditriphenylphospholorium dichloride were dissolved in 5mL of chloroform, stirred at room temperature for 3 hours, then 2,2' -azobis (2-methylpropanenitrile) (AIBN, 10 mg) was added, and the mixture was transferred to an autoclave at 80℃to react for 24 hours, and tetrahydrofuran was removed by suction filtration to obtain Pd 1 @POL-1 as a white solid.
The general formula of the double tin addition reaction of the catalytic terminal alkyne in the step 2) is as follows:
The double tin addition reaction process of the catalytic terminal alkyne comprises the following steps: 15.5mg of Pd 1 @ POL-1 was added to a dry, branched reaction tube under nitrogen atmosphere, the tube was sealed with a rubber septum, and 2mL of distilled tetrahydrofuran was added followed by 1 equivalent of alkyne, 1 equivalent of tributyltin hydride was added dropwise to the tube, 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, suction filtered, and the crude product was purified directly by silica gel column chromatography eluting with petroleum ether, ethyl acetate and 1% triethylamine to give the corresponding Z-configuration ditin substituted olefin product.
According to the technical scheme, a monoatomic palladium phosphine ligand porous polymer is used as a catalyst, and double-stannation reaction of high regioselectivity and chemical selectivity of alkyl hydrogen stannate and terminal alkyne is realized under heterogeneous conditions, so that a1, 2-ditin substituted olefin product with a single configuration (Z-type) is obtained.
According to the technical scheme, tributyl tin hydride with low price is adopted as a tin source, so that the cost of the reaction is reduced; the reaction utilizes the enrichment effect of the polymer pore canal, which is beneficial to improving the activity and selectivity of the reaction; the reaction catalyst adopts the monoatomic palladium metallized phosphine ligand porous polymer, which is beneficial to preventing agglomeration of metal particles, not only can be recycled and reused, but also further improves the chemical selectivity of the reaction and promotes the generation of Z-type-1, 2-stannous substituted olefin products.
The method has low cost and high selectivity, and can realize double-stannation reaction of high regioselectivity and chemical selectivity of alkyl hydrogen stannate and terminal alkyne under heterogeneous condition to obtain 1, 2-ditin substituted olefin product with single configuration, namely Z-configuration.
Drawings
FIG. 1 is a hydrogen spectrum of (Z) -5, 6-bis (tributylstannyl) hex-5-en-1-ol in the example;
FIG. 2 is a carbon spectrum of (Z) -5, 6-bis (tributylstannyl) hex-5-en-1-ol in the 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 the examples;
FIG. 6 is a carbon spectrum of (Z) - (1- (4-nitrophenyl) ethylene-1, 2-diyl) bis (tributylstannane) in the examples;
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 the examples;
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 the examples.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but is not limited thereto.
Example 1:
Taking 4-pentyn-1-ol as an example, a double tin reaction occurs to produce (Z) -5, 6-bis (tributylstannyl) hex-5-en-1-ol, the reaction equation is as follows:
the preparation method comprises the following specific preparation steps:
(a) The catalyst has the general formula:
(b) 15.5mg of Pd 1 @ POL-1 was added to a dry, branched reaction tube under nitrogen atmosphere, 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 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, suction 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) -5, 6-bis (tributylstannyl) hex-5-en-1-ol in a yield of 72% with selectivity a: b=50:1.
Example 2:
Taking 1- (2-propyne) -1H-indole as an example, a double tin 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 preparation steps:
(a) The catalyst synthesis general formula is the same as in example 1;
(b) 15.5mg of Pd 1 @ POL-1 was added to a dry, branched reaction tube under nitrogen atmosphere, the vial was sealed with a rubber septum, and 2mL of distilled tetrahydrofuran was added followed by 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 complete, the solution was filtered, washed with ethyl acetate, suction 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- (2, 3-bis (tributylstannyl) allyl) -1H-indole in 89% yield with a total selectivity c: d=100:1.
Example 3:
Taking p-nitrophenylacetylene as an example, a double tin reaction occurs to generate (Z) - (1- (4-nitrophenyl) ethylene-1, 2-diyl) bis (tributylstannane), and the reaction equation is as follows:
the preparation method comprises the following specific preparation steps:
(a) The catalyst synthesis general formula is the same as in example 1;
(b) 15.5mg of Pd 1 @ POL-1 was added to a dry, branched reaction tube under nitrogen atmosphere, the vial was sealed with a rubber septum, and 2mL of distilled tetrahydrofuran was added followed by 0.5mmol of p-nitrophenylacetylene, 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 to completion, the solution was filtered and washed with ethyl acetate, suction 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, selectivity e: f=100:1.
Example 4:
taking clodinafop-propargyl acid as an example, a double tin reaction is carried out to generate (Z) -2, 3-bis (tributylstannyl) allyl (R) -2- (4- ((5-chloro-3-fluoropyridin-2-yl) oxy) phenoxy) propionate, and the reaction equation is as follows:
the preparation method comprises the following specific preparation steps:
(a) The catalyst synthesis general formula is the same as in example 1;
(b) 15.5mg of Pd 1 @ POL-1 was added to a dry, branched reaction tube under nitrogen atmosphere, the vial was sealed with a rubber septum, and 2mL of distilled tetrahydrofuran was added followed by 0.5mmol of clodinamic acid, 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 to completion, the solution was filtered and washed with ethyl acetate, suction 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) -2, 3-bis (tributylstannyl) allyl (R) -2- (4- ((5-chloro-3-fluoropyridin-2-yl) oxy) phenoxy) propionate in 83% yield, selectivity g: h=50:1.
As shown in fig. 1-8, the nuclear magnetic resonance and mass spectrometry characterization data of the 1, 2-ditin substituted olefin products of the several Z-configurations described above 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 tin product to the tin hydrogenation product is as high as more than 100:1, which is far higher than the reported value of the current literature.
Claims (3)
1. A process for preparing a Z-configuration-1, 2-ditin substituted olefin using a monoatomic palladium phosphine ligand comprising the steps of:
1) 100mg of tris (2-methoxy-5-vinylphenyl) phosphine and 12mg of ditriphenylphosphole palladium dichloride were dissolved in 5mL of chloroform, stirred at room temperature for 3 hours, followed by addition of 10mg of 2,2' -azobis (2-methylpropanenitrile), and the mixture was transferred to an autoclave at 80℃to react for 24 hours, tetrahydrofuran was removed by suction filtration, to obtain a white solid Pd 1 @ POL-1;
2) The 1, 2-ditin substituted olefin product with Z-configuration is prepared by adopting a diatomic palladium phosphine ligand porous polymer to catalyze the double tin addition reaction of terminal alkyne: 15.5mg of Pd 1 @ POL-1 was added to a dry, branched reaction tube under nitrogen atmosphere, the tube was sealed with a rubber septum, and 2mL of distilled tetrahydrofuran was added followed by 1 equivalent of alkyne, 1 equivalent of tributyltin hydride was added dropwise to the tube, 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, suction filtered, and the crude product was purified directly by silica gel column chromatography eluting with petroleum ether, ethyl acetate and 1% triethylamine to give the corresponding Z-configuration ditin substituted olefin product.
2. The method for preparing a Z-configuration-1, 2-ditin substituted olefin using a monoatomic palladium phosphine ligand according to claim 1, wherein the synthesis formula of the monoatomic palladium phosphine ligand porous polymer catalyst Pd 1 @ POL-1 in step 1) is:
The preparation process of the monoatomic palladium phosphine ligand porous polymer catalyst Pd 1 @POL-1 comprises the following steps: 100mg of S1 in the general formula, i.e., tris (2-methoxy-5-vinylphenyl) phosphine and 12mg of ditriphenylphospholorium dichloride were dissolved in 5mL of chloroform, stirred at room temperature for 3 hours, followed by addition of 10mg of 2,2' -azobis (2-methylpropanenitrile), and the mixture was transferred to an autoclave at 80℃for reaction for 24 hours, and tetrahydrofuran was removed by suction filtration to obtain Pd 1 @ POL-1 as a white solid.
3. The method for preparing a Z-configuration-1, 2-ditin substituted olefin using a monoatomic palladium phosphine ligand according to claim 1, wherein the double stannation addition reaction of the catalytic terminal alkyne in step 2) has the general formula:
The double tin addition reaction process of the catalytic terminal alkyne comprises the following steps: 15.5mg of Pd 1 @ POL-1 was added to a dry, branched reaction tube under nitrogen atmosphere, the tube was sealed with a rubber septum, and 2mL of distilled tetrahydrofuran was added followed by 1 equivalent of alkyne, 1 equivalent of tributyltin hydride was added dropwise to the tube, 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, suction filtered, and the crude product was purified directly by silica gel column chromatography eluting with petroleum ether, ethyl acetate and 1% triethylamine to give the corresponding Z-configuration ditin substituted olefin product.
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