CN104710476A - Chiral bidentate phosphite ligand and preparation method and application thereof - Google Patents

Chiral bidentate phosphite ligand and preparation method and application thereof Download PDF

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CN104710476A
CN104710476A CN201310686020.4A CN201310686020A CN104710476A CN 104710476 A CN104710476 A CN 104710476A CN 201310686020 A CN201310686020 A CN 201310686020A CN 104710476 A CN104710476 A CN 104710476A
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reaction
ligand
mol ratio
chiral
diketone
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王来来
逄增波
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The invention discloses a chiral bidentate phosphite ligand and a preparation method and an application thereof. The chiral bidentate phosphite ligand is a white foam solid. The ligand has characteristics of simple synthetic route, low cost, good stability in air and the like. A metallic copper complex of the ligand has high catalytic activity and optical selectivity to 1,4-conjugated addition of cycloenones.

Description

Chiral bidentate phosphite ligand and preparation method and purposes
Technical field
The present invention relates to the derivative chiral bidentate phosphite ligand of a kind of tartrate and synthetic method thereof, be applied to prepare part/Cu complex compound catalyst, catalysis organic zinc reagent is to the asymmetric Isosorbide-5-Nitrae-conjugate addition reaction of ring-type ketenes, and synthesis has optically active beta-ethyl cyclic ketone.
Background technology
Alkyl or aryl zincon is to α, 1 of beta-unsaturated carbonyl compound, 4-conjugate addition is one of important reaction forming C-C key, asymmetric 1, 4-conjugate addition reaction can synthesize the medicine or intermediate with physiologically active, as muskone ((R)-Muscone), mycobacteria reagent (erogorgiaene), anticancer class medicine (Clavularin B), cardiovascular disease therapies medicine (PGE1), noncompetitive blockers ((-)-pumiliotoxin C), and Ibuprofen BP/EP [(+)-ibuprofen]. therefore, in recent years, this reaction is subject to extensive concern and further investigation.
Design and synthesis can form the chiral ligand of complex compound catalyst with metal, is the key realizing efficient asymmetric Isosorbide-5-Nitrae-conjugate addition reaction.1993, asymmetric Isosorbide-5-Nitrae-conjugate addition reaction that Alexakis reported first copper-phosphorus (III) is ligand complex catalyzed.[Alexakis, A.; Frutos, J.; Mangeney, P. Tetrahedron:Asymmetry 1993,4,2427-2430.] since then, many chiral phosphorus ligand (such as: chiral phosphoramidite ester part, chirality phosphite ester ligand, chirality P, O and P, N part etc.) are successfully applied in this reaction.[Perez H F, Etayo P, Panossian A, Ferran A V. Chem. Rev. 2011,111,3,2119-2176.], these parts have had more than one piece patent application open, as [US 20070259774 A1, US 20090124836A1, US7728177B2, EP 1884509 A1, CN 101565436 A, CN 101090904 A.]
At present, existing outstanding chiral ligand not all has high asymmetric induction ability to multiple α, β-Unsaturated Alkenone substrate; And this reaction often needs specific reaction conditions just can provide higher enantioselectivity.Therefore, design and synthesis chiral phosphorus ligand and applied research in the reaction still significant.
Summary of the invention
The object of this invention is to provide the chiral bidentate phosphite ligand that a kind of tartrate is derivative.
Another object of the present invention is to provide the synthetic method of above-mentioned part.
A further object of the present invention is to provide the purposes of above-mentioned part.
A kind of chiral bidentate phosphite ligand, general structure such as formula shown in I,
I
In part group be:
。
 
Chiral bidentate phosphite ligand of the present invention, is selected from the one in formula II to VI,
。
Chiral bidentate phosphite ligand of the present invention is white solid foam.
A preparation method for chiral bidentate phosphite ligand, is characterized in that:
Under normal pressure nitrogen atmosphere, in tetrahydrofuran (THF) (THF) solvent, with (3R, 4R)-1-benzyl-3 that (L)-tartrate is derivative, sub-phosphoryl chloride, DMAP (DMAP) and triethylamine (NEt that 4-dihydroxy-pyridine ring-2,5-diketone, xenol are derivative 3) be reactant, react 0.5 ~ 4 hour at-10 DEG C to-15 DEG C; After reaction terminates, removal of solvent under reduced pressure, adds toluene, after fully stirring, and elimination insolubles, after filtrate is concentrated, through column chromatography for separation, synthesis of chiral phosphite ester ligand.
Reactant (3R, 4R)-1-benzyl-3,4-dihydroxy-pyridine ring-2,5-diketone of the present invention is 1:2 ~ 4 with the mol ratio of the sub-phosphoryl chloride that (R) or (S)-xenol derive.
Reactant DMAP of the present invention is 1:4 ~ 5 with the mol ratio of (3R, 4R)-1-benzyl-3,4-dihydroxy-pyridine ring-2,5-diketone.
The mol ratio of reactant (3R, 4R)-1-benzyl-3,4-dihydroxy-pyridine ring-2,5-diketone of the present invention and triethylamine is 1:2 ~ 4.
Chirality phosphite ester ligand of the present invention and metallic copper precursor reaction in－situ Kaolinite Preparation of Catalyst, catalysis organic zinc to the asymmetric Isosorbide-5-Nitrae-conjugate addition reaction of α, β-Unsaturated Alkenone, synthesis of optically active beta substitution ketone product.
Illustrate the asymmetric Isosorbide-5-Nitrae-conjugate addition reaction process of organic zinc to α, β-Unsaturated Alkenone as follows:
Under normal pressure nitrogen atmosphere, in organic solvent, described part and Cu salt reaction in－situ one hour, prepare part-Cu catalyzer.Then add α successively wherein, β-Unsaturated Alkenone and organic zinc, react 4 ~ 12 hours at-20-20 DEG C; After reaction terminates, add distilled water and dilute hydrochloric acid solution cancellation reaction in the reactive mixture, be extracted with ethyl acetate, merge organic phase, use saturated NaHCO successively 3solution, saturated common salt water washing, anhydrous Na 2sO 4drying, filters, concentrated, and synthesis has optically active β-ethyl cyclic ketone product, gas-chromatography (GC) assay products.
Described Cu salt is selected from copper trifluoromethanesulfcomposite [Cu (OTf) 2], trifluoromethanesulfonic acid cuprous [(CuOTf) 2c 6h 6] or Cu (OAc) 2h 2o, wherein OTf -1it is trifluoromethanesulfonic acid root; The mol ratio of Cu salt and part is 1:1 ~ 3; Organic solvent is selected from tetrahydrofuran (THF), ether, toluene or methylene dichloride; Temperature of reaction is-20 ~ 20 DEG C; Reaction times is 4 ~ 12 hours.
Described ring-type ketenes is selected from 2-cyclopentenone, 2-cyclonene or 2-suberene ketone; The mol ratio of part/Cu catalyzer, ring-type ketenes and organic zinc is 1:50:120.
The xenol that the present invention mentions does not have chirality, and compare with the normally used chiral binaphthol of synthesizing phosphorous acid ester part, low price, easily carries out its chemically modified; Chirality phosphite ester ligand has the features such as synthetic route is simple, cost is low, stable in the air, and the Isosorbide-5-Nitrae-conjugate addition reaction of its metallic copper complex compound to annulenones has high catalytic activity and optical selective.Apply this chiral ligand, the medicine or intermediate with physiologically active can be prepared by asymmetric Isosorbide-5-Nitrae-conjugate addition reaction, in the industries such as medicine, agricultural chemicals, spices and natural chiral Product formation, there is important using value.
Embodiment
Embodiment 1 ~ 5: prepare chiral bidentate phosphite ligand.
Embodiment 6 ~ 25: part-Cu catalyst preparing and the application in the asymmetric Isosorbide-5-Nitrae-addition reaction of organic zinc to annulenones thereof.
Embodiment 1: preparation chirality phosphite ester ligand, structural formula is as follows:
Under normal pressure nitrogen atmosphere, in the 100mL Xiu Langke bottle that magneton is housed, add (3R, 4R)-1-benzyl-3,4-dihydroxy-pyridine ring-2,5-diketone (294.7mg, 1.33mmol), sub-phosphoryl chloride (734.6mg, 2.93 mmol) and DMAP (35.8mg, 0.3mmol), add 10 mL tetrahydrofuran (THF)s and make solvent, stir and solid is dissolved completely, solution is chilled to-15 DEG C, slowly drips triethylamine 0.56mL and react 0.5 h at keeping-15 DEG C.Removal of solvent under reduced pressure, adds 20 mL toluene and fully stirs, filtering solid, and after filtrate is concentrated, obtain part 225.2 mg through dodging chromatographic separation, yield is 26.02 %.
White foam solid. 31P NMR (161MHz, CDCl 3): δ 143.96; 1HNMR (400 MHz, CDCl 3): δ4.58 (d, J= 12.6 Hz, 2H), 5.06 (q, J= 3.8 Hz, 2H), 7.04 (d, J= 7.8 Hz, 2H)，7.18 (d, J= 2.2 Hz, 2H)，7.21 – 7.19 (m, 2H)，7.22 (t, J= 3.7 Hz, 3H)，7.24 (d, J= 5.2 Hz, 4H)，7.30 (td, J= 7.4, 4.4 Hz, 3H)，7.35 (dd, J= 9.8, 4.7 Hz, 4H)，7.48 – 7.41 (m, 1H); 13C NMR (100 MHz, CDCl 3): δ 42.03，74.38，121.02，121.54, 124.27，127.20，128.01, 128.82，128.99， 129.66，133.45，147.60，168.74.
Embodiment 2: preparation chirality phosphite ester ligand, structural formula is as follows:
With the method in embodiment 1, (3R, 4R)-1-benzyl-3,4-dihydroxy-pyridine ring-2,5-diketone (201.1mg, 0.91 mmol), sub-phosphoryl chloride (612mg, 2.0 mmol) and DMAP (24.4mg, 0.15mmol), triethylamine 0.42 mL, the reaction times is 4 hours.All the other obtain ligand 1 89.4mg with embodiment 1, yield 27.37%.
White foam solid. 31P NMR (161MHz, CDCl 3): δ 146.42; 1HNMR (400 MHz, CDCl 3): δ2.31 (d, J= 3.0 Hz, 12H), 2.33 (s, 7H), 2.35 (s, 5H), 4.67 (s, 2H), 5.12 – 5.07 (m, 2H), 7.00 (d, J= 11.6 Hz, 4H), 7.07 – 7.03 (m, 4H), 7.29 – 7.26 (m, 3H), 7.35 (dd, J= 6.6, 2.9 Hz, 2H); 13C NMR (100 MHz, CDCl 3): δ 14.14，20.83，43.01，75.90，127.87，128.08，130.09，130.45，131.19，131.24，134.28，134.46，144.84，145.31，170.30.
Embodiment 3: preparation chirality phosphite ester ligand, structural formula is as follows:
With the method in embodiment 1, (3R, 4R)-1-benzyl-3,4-dihydroxy-pyridine ring-2,5-diketone (100.5mg, 0.45 mmol), sub-phosphoryl chloride (474.3mg, 1.0 mmol) and DMAP (12.2mg, 0.1mmol), triethylamine 0.21mL, the reaction times is 0.5 hour.All the other obtain part 288.7mg with embodiment 1, yield 15.37%.
White foam solid. 31P NMR (161MHz, CDCl 3): δ146.92 ; 1HNMR (400 MHz, CDCl 3): δ1.23 – 1.08 (m, 48H)，1.45 – 1.36 (m, 24H)，4.65 – 4.51 (m, 2H)，5.07 (d, J= 6.2 Hz, 2H)，7.10 – 7.03 (m, 6H)，7.15 (dd, J= 11.0, 4.0 Hz, 5H)，7.35 (t, J= 7.3 Hz, 2H); 13C NMR (100 MHz, CDCl 3): δ28.71，33.50，33.65，34.40，41.95，74.58，123.21，124.28，125.47，127.20，127.67，128.01，136.81，138.99，145.48，145.80，169.35.
Embodiment 4: preparation chirality phosphite ester ligand, structural formula is as follows:
With the method in embodiment 1, (3R, 4R)-1-benzyl-3,4-dihydroxy-pyridine ring-2,5-diketone (100.5mg, 0.45 mmol), sub-phosphoryl chloride (385.8mg, 1.0 mmol) and DMAP (12.2mg, 0.1mmol), triethylamine 0.21 mL, the reaction times is 0.5 hour.All the other obtain part 268.5mg with embodiment 1, yield 32.08%.
White foam solid. 31P NMR (161MHz, CDCl 3): δ151.23; 1HNMR (400 MHz, CDCl 3): δ4.63 (d, J= 15.2 Hz, 2H), 5.22 (d, J= 5.8 Hz, 2H)，7.10 – 7.08 (m, 3H)，7.11 (d, J= 2.3 Hz, 4H)，7.16 (d, J= 2.0 Hz, 2H)，7.23 – 7.21 (m, 4H); 13C NMR (100 MHz, CDCl 3): δ 42.38，75.15，124.27，127.20，127.89，128.01, 128.27，128.91，129.28， 129.35，133.12，146.47，168.28.
Embodiment 5: preparation chirality phosphite ester ligand, structural formula is as follows:
With the method in embodiment 1, (3R, 4R)-1-benzyl-3,4-dihydroxy-pyridine ring-2,5-diketone (201.1mg, 0.91 mmol), sub-phosphoryl chloride (1.1233g, 2.0 mmol) and DMAP (24.4mg, 0.2mmol), triethylamine 0.42 mL, the reaction times is 4 hours.All the other obtain ligand 1 77.8mg with embodiment 1, yield 15.37%.
White foam solid. 31P NMR (161MHz, CDCl 3): δ150.84; 1HNMR (400 MHz, CDCl 3): δ4.66 (dd, J= 32.8, 13.9 Hz, 2H)，5.26 (d, J= 5.1 Hz, 2H)，7.28 – 7.22 (m, 3H)，7.36 (dd, J= 6.3, 3.1 Hz, 2H)，7.40 (d, J= 1.3 Hz, 4H)，7.68 (dt, J= 14.3, 7.1 Hz, 4H); 13C NMR (100 MHz, CDCl 3): δ 42.40，75.23，116.86，117.35，127.20，127.65， 127.95，128.01， 133.10，134,91，134.97，144.47，168.48.
Embodiment 6:
In a nitrogen atmosphere, Cu (OTf) 2(0.005 mmol, 1.8 mg) and the part described in embodiment 1 (0.01 mmol, 6.5 mg) are dissolved in 4 mL toluene, and stirring at room temperature 1 h, obtains the solution of part-Cu catalyzer.Be cooled to 0 DEG C, add 2-cyclonene (0.25 mmol, 25 μ L) successively, zinc ethyl (hexane solution of 1 mol/L, 0.6 mL), react 4 hours at 0 DEG C.Add 2 mL distilled water and 2 mL dilute hydrochloric acid solutions (2.0 mol/L) cancellation reaction, be extracted with ethyl acetate (5 mL × 3), merge organic phase, use saturated NaHCO successively 3solution, saturated common salt water washing, anhydrous Na 2sO 4drying, filters, concentrated, and analyze through gas-chromatography (GC), transformation efficiency is 47 %, and enantioselectivity is 59%, and product absolute configuration is S.
Embodiment 7:
With embodiment 6, part is selected from the part (0.01 mmol, 7.6 mg) described in embodiment 2, and it is 99 % that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 17 %, and product absolute configuration is S.
Embodiment 8:
With embodiment 6, part is selected from the part (0.01 mmol, 11.0 mg) described in embodiment 3, and it is 99% that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 26%, and product absolute configuration is S.
Embodiment 9:
With embodiment 6, part is selected from the part (0.01 mmol, 9.2 mg) described in embodiment 4, and it is 49 % that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 5 %, and product absolute configuration is S.
Embodiment 10:
With embodiment 6, part is selected from the part (0.01 mmol, 12.7 mg) described in embodiment 5, and it is 99 % that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 5 %, and product absolute configuration is R.
Embodiment 11:
With embodiment 6, mantoquita is selected from Cu (OAc) 2h 2it is 99% that O (0.005mmol, 1mg), GC analyze display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 40 %, and product absolute configuration is S.
Embodiment 12:
With embodiment 6, mantoquita is selected from (CuOTf) 2c 6h 6(0.0025 mmol, 1.25 mg), it is 33 % that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 37 %, and product absolute configuration is S.
Embodiment 13:
With embodiment 6, solvent is selected from ether 4ml, and it is 92 % that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 41 %, and product absolute configuration is S.
Embodiment 14:
With embodiment 6, solvent is selected from ether 4ml, and it is 92 % that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 41 %, and product absolute configuration is S.
Embodiment 15:
With embodiment 6, solvent is selected from methylene dichloride 4ml, and it is 81 % that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 8 %, and product absolute configuration is S.
Embodiment 16:
With embodiment 6, solvent is selected from tetrahydrofuran (THF) 4ml, and it is 68% that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 42 %, and product absolute configuration is S.
Embodiment 17:
With embodiment 6, solvent is selected from the mixed solvent of tetrahydrofuran (THF) 2ml and ether 2ml, and it is 50 % that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 75 %, and product absolute configuration is S.
Embodiment 18:
With embodiment 6, temperature of reaction is 20 oit is 99% that C, GC analyze display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 49%, and product absolute configuration is S.
Embodiment 19:
With embodiment 6, temperature of reaction is-10 oit is 44% that C, GC analyze display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 65%, and product absolute configuration is S.
Embodiment 20:
With embodiment 6, temperature of reaction is-20 oit is 72% that C, GC analyze display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 48%, and product absolute configuration is S.
Embodiment 21:
With embodiment 6, the reaction times is 8 hours, and it is 99% that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 32%, and product absolute configuration is S.
Embodiment 22:
With embodiment 6, the reaction times is 12 hours, and it is 83% that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 69%, and product absolute configuration is S.
Embodiment 23:
With embodiment 6, part consumption (0.0025mmol, 1.6mg) as described in Example 1, it is 99 % that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 40%, and product absolute configuration is S.
Embodiment 24:
With embodiment 6, part consumption (0.015mmol, 9.7mg) as described in Example 1, it is 13 % that GC analyzes display product 3-ethyl cyclohexanone transformation efficiency, and enantioselectivity is 49%, and product absolute configuration is S.
Embodiment 25:
With embodiment 6, annulenones substrate is selected from 2-cyclopentenone (0.25 mmol, 0.022 mL).It is 93% that GC analyzes display product 3-ethylcyclopentanone transformation efficiency, and enantioselectivity is 50%, and product absolute configuration is R.

Claims (9)

1. a chiral bidentate phosphite ligand, general structure such as formula shown in I,
I
In part group be:
。
2. part as claimed in claim 1, is characterized in that chiral bidentate phosphite ligand, is selected from the one in formula II to VI,
。
3. the preparation method of a kind of chiral bidentate phosphite ligand as claimed in claim 1 or 2, is characterized in that:
Under normal pressure nitrogen atmosphere, in tetrahydrofuran (THF) (THF) solvent, with (3R, 4R)-1-benzyl-3 that (L)-tartrate is derivative, sub-phosphoryl chloride, DMAP (DMAP) and triethylamine (NEt that 4-dihydroxy-pyridine ring-2,5-diketone, xenol are derivative 3) be reactant, react 0.5 ~ 4 hour at-10 DEG C to-15 DEG C; After reaction terminates, removal of solvent under reduced pressure, adds toluene, after fully stirring, and elimination insolubles, after filtrate is concentrated, through column chromatography for separation, synthesis of chiral phosphite ester ligand.
4. method as claimed in claim 3, is characterized in that the mol ratio of the sub-phosphoryl chloride that reactant (3R, 4R)-1-benzyl-3,4-dihydroxy-pyridine ring-2,5-diketone derives with (R) or (S)-xenol is 1:2 ~ 4.
5. method as claimed in claim 3, is characterized in that reactant DMAP is 1:4 ~ 5 with the mol ratio of (3R, 4R)-1-benzyl-3,4-dihydroxy-pyridine ring-2,5-diketone.
6. method as claimed in claim 3, is characterized in that the mol ratio of reactant (3R, 4R)-1-benzyl-3,4-dihydroxy-pyridine ring-2,5-diketone and triethylamine is 1:2 ~ 4.
7. the application of part as claimed in claim 1 or 2, it is characterized in that chirality phosphite ester ligand and metallic copper precursor reaction in－situ Kaolinite Preparation of Catalyst, catalysis organic zinc is to asymmetric 1 of α, β-Unsaturated Alkenone, 4-conjugate addition reaction, synthesis of optically active beta substitution ketone product.
8. the application of part as claimed in claim 7, under it is characterized in that normal pressure nitrogen atmosphere, in organic solvent, described part and Cu salt reaction in－situ one hour, prepare part-Cu catalyzer; Then add α successively wherein, β-Unsaturated Alkenone and organic zinc, react 4 ~ 12 hours at-20-20 DEG C; After reaction terminates, add distilled water and dilute hydrochloric acid solution cancellation reaction in the reactive mixture, be extracted with ethyl acetate, merge organic phase, use saturated NaHCO successively 3solution, saturated common salt water washing, anhydrous Na 2sO 4drying, filters, concentrated, and synthesis has optically active β-ethyl cyclic ketone product, gas-chromatography (GC) assay products.
9. the application of part as claimed in claim 8, is characterized in that described Cu salt is selected from copper trifluoromethanesulfcomposite [Cu (OTf) 2], trifluoromethanesulfonic acid cuprous [(CuOTf) 2c 6h 6] or Cu (OAc) 2h 2o, wherein OTf -1it is trifluoromethanesulfonic acid root; The mol ratio of Cu salt and part is 1:1 ~ 3; Organic solvent is selected from tetrahydrofuran (THF), ether, toluene or methylene dichloride; Temperature of reaction is-20 ~ 20 DEG C; Reaction times is 4 ~ 12 hours; Described ring-type ketenes is selected from 2-cyclopentenone, 2-cyclonene or 2-suberene ketone; The mol ratio of part/Cu catalyzer, ring-type ketenes and organic zinc is 1:50:120.
CN201310686020.4A 2013-12-16 2013-12-16 Chiral bidentate phosphite ligand and preparation method and application thereof Pending CN104710476A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110813380A (en) * 2019-09-29 2020-02-21 浙江工业大学 Copper ketone complex catalyst, preparation method thereof and application thereof in acetylene hydrochlorination
CN111203277A (en) * 2020-02-27 2020-05-29 郑州大学 Application of chiral bidentate phosphite ligand, Conia-Ene reaction catalyst and method for constructing chiral quaternary carbon center
CN111203276A (en) * 2020-02-27 2020-05-29 郑州大学 Application of chiral bidentate phosphite ligand, hydrosilation reaction catalyst and application thereof, and preparation method of chiral silane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AI-PING XING等: ""Chiral phosphite ligands derived from L-(+)-tartaric acid: synthesis and application in the Cu-catalyzed 1,4-conjugate addition of organozincs to cyclic enones"", 《TETRAHEDRON》 *
GODFRIED J. H. BUISMAN等: ""Hydridorhodium Diphosphite Catalysts in the Asymmetric Hydroformylation of Styrene"", 《J. CHEM. SOC. DALTON TRANS.》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110813380A (en) * 2019-09-29 2020-02-21 浙江工业大学 Copper ketone complex catalyst, preparation method thereof and application thereof in acetylene hydrochlorination
CN110813380B (en) * 2019-09-29 2022-04-19 浙江工业大学 Copper ketone complex catalyst, preparation method thereof and application thereof in acetylene hydrochlorination
CN111203277A (en) * 2020-02-27 2020-05-29 郑州大学 Application of chiral bidentate phosphite ligand, Conia-Ene reaction catalyst and method for constructing chiral quaternary carbon center
CN111203276A (en) * 2020-02-27 2020-05-29 郑州大学 Application of chiral bidentate phosphite ligand, hydrosilation reaction catalyst and application thereof, and preparation method of chiral silane
CN111203276B (en) * 2020-02-27 2022-11-18 郑州大学 Application of chiral bidentate phosphite ligand, hydrosilation reaction catalyst and application thereof, and preparation method of chiral silane

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Application publication date: 20150617