CN109776253B - Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing semi-reduction of alkyne through palladium hydrogen donor by alcohol - Google Patents
Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing semi-reduction of alkyne through palladium hydrogen donor by alcohol Download PDFInfo
- Publication number
- CN109776253B CN109776253B CN201811607534.5A CN201811607534A CN109776253B CN 109776253 B CN109776253 B CN 109776253B CN 201811607534 A CN201811607534 A CN 201811607534A CN 109776253 B CN109776253 B CN 109776253B
- Authority
- CN
- China
- Prior art keywords
- alkyne
- dosage
- alcohol
- reduction reaction
- molar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for selectively synthesizing cis-olefin and trans-olefin by catalyzing semi-reduction of alkyne with palladium under hydrogen supply of alcohol, which comprises the following steps: TEOA, NaOAc, a catalyst, alcohol and alkyne are subjected to reduction reaction of alkyne in an organic solvent to generate cis-form alkene; carrying out reduction reaction of alkyne on ligand, catalyst, alcohol and alkyne in an organic solvent to generate trans-olefin; the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 120-150 ℃, and the time of the reduction reaction is 20-48 h; the dosage of the catalyst is 5-20% of the molar dosage of alkyne, and the dosage of the alcohol is 10-100 times of the molar dosage of alkyne; the dosage of R, R-DIPAMP is 0.5-5 times of the molar dosage of alkyne. In the invention, the catalyst system has extremely high chemical reaction and stereoselectivity, and can synthesize cis-form or trans-form olefin products with high yield; the catalytic system has strong universality to a substrate, and alkynes containing various functional groups can efficiently carry out high-selectivity reduction reaction.
Description
Technical Field
The invention belongs to the technical field of catalytic synthesis of fine chemical products, and particularly relates to a method for selectively synthesizing cis-olefin and trans-olefin by catalyzing semi-reduction of alkyne with palladium under hydrogen supply of alcohol.
Background
The conjugated olefin compound is an important intermediate for synthesizing medicaments, photoelectric materials and the like, and the 1, 2-toluylene compound is a very important compound. For example, many compounds containing 1, 2-stilbene structural units which have various biological activities (anti-tumor, anti-angiogenic, cytotoxic, cell proliferation-preventing, etc.) are isolated from natural products. For example, the cis-structure Combretastatin A-4 is a good anti-tumor drug and is likely to become the first drug on the market in anti-tubulin polymerization drugs. Resveratrol in trans-structure has very good antioxidant compounds. In addition, the compound is also a phenylethynyl hydrazine Sulfate Salt which is synthesized by taking styrene with end group as a raw material and has antidepressant action.
The reduction reaction synthesis method of alkyne mainly comprises the following steps: hydrogen supply, formic acid hydrogen supply and ammonia borane hydrogen supply direct reduction method. Catalyst Pd-CaCO for the first time used in Lindlar of Germany in 1952 3-PbO and Pd-BaS2O4Quinoline, two, which catalyzes hydrogen to selectively reduce alkynes to cis-alkenes, is widely used in synthetic chemistry, but has three problems: (1) the preparation method of the Lindlar catalyst determines the catalytic activity of the catalyst, and the reduction reaction using the Lindlar catalyst usually cannot avoid the over-reduction reaction of alkyne, namely the reaction of reducing alkyne into saturated alkane, so that the selectivity (chemical reaction selectivity) of the reduction reaction is not ideal, and the separation and purification of products become difficult; (2) the conventional hydrogen is used as a hydrogen source for the reduction reaction, and special requirements are required in the aspects of using a reactor and safety; (3) trans olefins cannot be obtained by this process. Therefore, the research of selectively reducing alkyne into olefin by using non-hydrogen source has been one of the hot and important research contents in the field of synthetic chemistry. In 2016, Kenan Tokmic was synthesized by (MesCCC) Co (N)2)(PPh3) The catalyst, alkyne reduction under hydrogen conditions to cis-form alkene, this method also has the above three problems.
Later in 2008, Elsevier used formic acid as the hydrogen source and NHC (N-heterocyclic carbene) as the ligand to stabilize the Pd (0) catalyst, thereby achieving the reduction of alkynes to cis-alkenes. The chemical reaction and the stereoselectivity are high, the yield of alkyne without heteroatom is high, and the reaction condition is relatively mild. The disadvantages are that the selectivity and yield for some substrates (such as 1,3 diyne, alkyne ester, etc.) is not ideal, trans olefins are difficult to obtain, and formic acid is expensive, especially ligand NHC is very expensive, limiting its large-scale use. Alami Et al reported silane Et 3SiH is used as a hydrogen source, diaryl alkyne is reduced into cis-diaryl alkene with high selectivity through a two-step method, and the process is in PtO2In the presence of a catalyst, firstAn addition product of hydrosilane and diarylalkyne is first formed, and then the silane group is removed under reflux in the presence of an equivalent amount of TBAF (tetrabutylammonium fluoride) to obtain cis-diarylene. Although the selectivity of the reaction system is high, the yield of the final olefin is not good due to the two-step reaction, and trans-olefin is also difficult to obtain due to the use of an equivalent amount of TBAF as a phase transfer catalyst, so that the reaction system is not practical.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for selectively synthesizing cis-olefin and trans-olefin by catalyzing alkyne semi-reduction through palladium hydrogen donor by alcohol, wherein the catalyst is cheap and easy to obtain, the reaction operation is simple, and the method is suitable for large-scale production; the cheap ethanol is used as a hydrogen source, so that the method is safe, economical, green and environment-friendly; the catalyst system has extremely high chemical reaction and stereoselectivity, and can synthesize cis-or trans-olefin products with high yield; the catalytic system has strong universality to a substrate, and alkynes containing various functional groups can efficiently carry out high-selectivity reduction reaction.
In order to solve the above technical problems, an embodiment of the present invention provides a method for selectively synthesizing cis-form olefin by semi-reduction of alkyne under the catalysis of palladium hydrogen donor with alcohol, comprising the following steps:
TEOA, NaOAc, a catalyst, alcohol and alkyne are subjected to reduction reaction of alkyne in an organic solvent to generate cis-form alkene;
the reduction reaction formula is:
the alkyne has a structural general formula as follows:
the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 120-150 ℃, and the time of the reduction reaction is 20-48 h;
the using amount of the catalyst is 5-20% of the molar using amount of alkyne, the using amount of the NaOAc is 0.5-5 times of the molar using amount of alkyne, the using amount of the TEOA is 0.5-5 times of the molar using amount of alkyne, and the using amount of the alcohol is 10-100 times of the molar using amount of alkyne;
wherein the organic solvent is acetonitrile;
the catalyst is selected from Pd (OAc)2、PdCl2Pd/C and PdCl2(PPh3)2At least one of (1).
Preferably, the catalyst is Pd (OAc)2The using amount is 10 percent of the molar using amount of alkyne;
the dosage of the NaOAc is 2 times of the molar dosage of alkyne, and the dosage of the TEOA is 2.5 times of the molar dosage of alkyne;
the alcohol is 95% ethanol, and the dosage is 50 times of the molar dosage of alkyne.
Preferably, the temperature of the reduction reaction is 140 ℃, and the reaction time is 30-40 h.
Wherein, in the structural general formula of the alkyne, R and R' are selected from any one of the following groups: alkyl, phenyl, naphthyl, pyridyl, alkylphenyl, alkoxyphenyl, halophenyl and silylphenyl.
The invention also provides a method for selectively synthesizing trans-olefin by catalyzing semi-reduction of alkyne with palladium under hydrogen supply of alcohol, which comprises the following steps: ligand R, R-DIPAMP, a catalyst, alcohol and alkyne are subjected to alkyne reduction reaction in an organic solvent to generate trans-olefin;
the reduction reaction formula is:
the alkyne has a structural general formula as follows:
the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 120-150 ℃, and the time of the reduction reaction is 20-48 h;
the dosage of the catalyst is 5-20% of the molar dosage of alkyne; the dosage of the R, R-DIPAMP is 0.5-5 times of the molar dosage of alkyne, the dosage of the NaOAc is 0.5-5 times of the molar dosage of alkyne, the dosage of the TEOA is 0.5-5 times of the molar dosage of alkyne, and the dosage of the alcohol is 10-100 times of the molar dosage of alkyne;
wherein the organic solvent is acetonitrile;
the catalyst is selected from Pd (OAc)2、PdCl2Pd/C and PdCl2(PPh3)2At least one of (a).
Preferably, the catalyst is Pd (OAc)2The using amount is 10 percent of the molar using amount of alkyne;
the dosage of the NaOAc is 2 times of the molar dosage of alkyne, and the dosage of the TEOA is 2.5 times of the molar dosage of alkyne;
the alcohol is 95% ethanol, and the dosage is 50 times of the molar dosage of alkyne.
Preferably, the temperature of the reduction reaction is 145 ℃, and the reaction time is 32-40 h.
Wherein, in the structural general formula of the alkyne, R and R' are selected from any one of the following groups: alkyl, phenyl, naphthyl, pyridyl, alkylphenyl, alkoxyphenyl, halophenyl and silylphenyl.
The invention also provides a method for reducing end group alkyne into olefin by palladium-catalyzed hydrogen supply through alcohol, which comprises the following steps:
under the protection of nitrogen (without oxygen), TEOA, NaOAc, a catalyst, alcohol and alkyne are subjected to reduction reaction of alkyne in an organic solvent to generate cis-form alkene;
the reaction formula is as follows:
the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 60-100 ℃, and the reaction time is 20-30 h;
the using amount of the catalyst is 5-20% of the mol using amount of alkyne, the using amount of the NaOAc is 0.5-5 times of the mol using amount of alkyne, the using amount of the TEOA is 0.5-5 times of the mol using amount of alkyne, and the using amount of the alcohol is 10-100 times of the mol using amount of alkyne;
the organic solvent is acetonitrile;
the catalyst is selected from Pd (OAc)2、PdCl2And PdCl2(PPh3)2At least one of (1).
Preferably, the catalyst is Pd (OAc) 2The using amount is 10 percent of the molar using amount of alkyne;
the dosage of the NaOAc is 2 times of the molar dosage of alkyne, and the dosage of the TEOA is 2.5 times of the molar dosage of alkyne;
the alcohol is 95% ethanol, and the dosage of the alcohol is 50 times of the molar dosage of alkyne.
Preferably, the temperature of the reduction reaction is 140 ℃ and the reaction time is 24 h.
In the structural general formula of the alkyne, R is selected from any one of the following groups: alkyl, benzene, naphthalene, pyridyl, alkylbenzene, alkoxybenzene, halobenzene and silylbenzene.
Preferably, the environment of the reduction reaction is under the protection of nitrogen.
The technical scheme of the invention has the following beneficial effects:
the innovation points of the invention are as follows: (1) the alcohol is used as a hydrogen source, so that the method is cheap, easy to obtain, safe, efficient, economic and environment-friendly; (2) cis-olefin and trans-olefin can be efficiently and selectively obtained, and the method is also applied to terminal alkyne synthesis to obtain terminal olefin.
The method for reducing alkyne into olefin provided by the invention has the following characteristics:
(1) the catalyst is cheap and easy to obtain, the reaction operation is simple, and the method is suitable for large-scale production;
(2) the cheap ethanol is used as a hydrogen source, so that the method is safe, economical, green and environment-friendly;
(3) the catalyst system has extremely high chemical reaction and stereoselectivity, and can synthesize cis-form or trans-form olefin products with high yield;
(4) The catalyst system has strong universality for substrates, and alkynes containing various functional groups can efficiently carry out high-selectivity reduction reaction.
Drawings
FIG. 1 is a hydrogen spectrum of a cis-stilbene as a target product obtained in example 1 of the present invention;
FIG. 2 is the respective carbon spectrograms of the target product cis-stilbene obtained in example 1 of the present invention;
FIG. 3 is a chart of hydrogen atoms of a cis-1-styrylnaphthalene benzene as a target product obtained in example 4 of the present invention;
FIG. 4 is a carbon spectrum diagram of a cis-1-styrylnaphthalene benzene as a target product obtained in example 4 of the present invention;
FIG. 5 is a chart of hydrogen spectra of cis-trimethyl (4-styrylphenyl) silane, a target product obtained in example 6 of the present invention;
FIG. 6 is a carbon spectrum of cis-trimethyl (4-styrylphenyl) silane, a target product obtained in example 6 according to the present invention;
FIG. 7 is a hydrogen spectrum of cis-1- (4-propylphenylethynyl) -4-methoxybenzene, the target product obtained in example 8 of the present invention;
FIG. 8 is a carbon spectrum of cis-1- (4-propylphenylethynyl) -4-methoxybenzene, the target product obtained in example 8 of the present invention;
FIG. 9 is a chart of hydrogen spectra of trans-stilbene which is a target product obtained in example 9 of the present invention;
FIG. 10 is a chart of carbon spectra of trans-stilbene as a target product in example 9 of the present invention;
FIG. 11 is a chart of hydrogen spectra of trans-stilbene as a target product in example 12 of the present invention;
FIG. 12 is a carbon spectrum of trans-stilbene of the desired product in example 12;
FIG. 13 is a hydrogen spectrum of trans-3-styrylpyridine of the target product obtained in example 15 of the present invention;
FIG. 14 is a carbon spectrum of trans-3-styrylpyridine as a target product in example 15 of the present invention;
FIG. 15 is a chart showing a hydrogen spectrum of trans-methyl phenylacrylate, a target product obtained in example 17 according to the present invention;
FIG. 16 is a carbon spectrum of trans-methyl phenylacrylate, a target product obtained in example 17 according to the present invention;
FIG. 17 is a chart showing a hydrogen spectrum of styrene as a target product obtained in example 19 of the present invention;
FIG. 18 is a carbon spectrum of styrene, a target product obtained in example 19 according to the present invention;
FIG. 19 is a hydrogen spectrum of a target product, 4-t-butylstyrene obtained in example 21 according to the present invention;
FIG. 20 is a carbon spectrum of a target product, 4-t-butylstyrene obtained in example 21 according to the present invention;
FIG. 21 is a chart of a hydrogen spectrum of a target product, 4-nitrostyrene, obtained in example 22 according to the present invention;
FIG. 22 is a carbon spectrum of 4-nitrostyrene, a target product obtained in example 22 of the present invention;
FIG. 23 is a hydrogen spectrum of 4-vinylbiphenyl, a target product obtained in example 24 of the present invention;
FIG. 24 is a carbon spectrum of 4-vinylbiphenyl, a target product obtained in example 24 of the present invention.
Detailed Description
To make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides a method for selectively synthesizing cis-olefin by catalyzing alkyne semi-reduction through palladium hydrogen donor by alcohol, which comprises the following steps:
TEOA, NaOAc, a catalyst, alcohol and alkyne are subjected to reduction reaction of alkyne in an organic solvent to generate cis-form alkene;
the reduction reaction formula is:
the alkyne has a structural general formula as follows:
the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 120-150 ℃, and the time of the reduction reaction is 20-48 h;
the using amount of the catalyst is 5-20% of the mol using amount of alkyne, the using amount of the NaOAc is 0.5-5 times of the mol using amount of alkyne, the using amount of the TEOA is 0.5-5 times of the mol using amount of alkyne, and the using amount of the alcohol is 10-100 times of the mol using amount of alkyne;
wherein the organic solvent is acetonitrile;
the catalyst is selected from Pd (OAc)2、PdCl2Pd/C and PdCl2(PPh3)2At least one of (a).
Preferably, the catalyst is Pd (OAc) 2The using amount is 10 percent of the molar using amount of alkyne;
the dosage of the NaOAc is 2 times of the molar dosage of alkyne, and the dosage of the TEOA is 2.5 times of the molar dosage of alkyne;
the alcohol is 95% ethanol, and the dosage of the alcohol is 50 times of the molar dosage of alkyne;
the temperature of the reduction reaction is 140 ℃, and the reaction time is 30-40 h.
Wherein, in the structural general formula of the alkyne, R and R' are selected from any one of the following genes: alkyl, benzene, naphthalene, pyridyl, alkylbenzene, alkoxybenzene, halobenzene and silylbenzene.
The following examples are provided to further illustrate the selective synthesis of cis-olefins by palladium-on-hydrogen catalysis of alkynes by alcohol semi-reduction.
Example 1
A15 ml pressure tube was charged with diphenylacetylene (0.20mmol), Pd (OAc)2(0.02mmol,4.48mg), NaOAc (0.40mmol,54.4mg), TEOA (0.75mmol,100L), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 140 ℃ for 32 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain the cis-stilbene, and the colorless liquid is 32.4mg, and the yield is 90 percent.
Fig. 1 shows a hydrogen spectrum of the target product cis-stilbene obtained in example 1, and fig. 2 shows respective carbon spectrums of the target product cis-stilbene obtained in example 1, and it can be seen from fig. 1 and 2 that the structure of the product is correct.
Example 2
1- (3-Chlorophenylethynyl) -3-methylbenzene (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), NaOAc (0.40mmol,54.4mg), TEOA (0.75mmol,100L), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 140 ℃ for 32 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product was purified by column chromatography to give cis-1- (3-chlorostyryl) -3-methylbenzene as a colorless liquid 43.8mg in 96% yield.
Example 3
1- (3-Fluorophenylethynyl) -3, 5-bis (trifluoromethyl) benzene (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), NaOAc (0.40mmol,54.4mg), TEOA (0.75mmol,100L), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 140 ℃ for 32 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product was purified by column chromatography to give cis-1- (3-fluorostyryl) -3, 5-bis (trifluoromethyl) benzene as a colorless liquid 65.5mg in 98% yield.
Example 4
1-Phenylethynylnaphthalene benzene (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube 2(0.02mmol,4.48mg), NaOAc (0.40mmol,54.4mg), TEOA (0.75mmol,100L), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 140 ℃ for 32 h.
After the reaction is finished, cooling to room temperature,ethyl acetate (10 mL) was added, and the organic phase was washed with saturated brine (3 times) and anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain the cis-1-styrylnaphthalene benzene, the colorless liquid is 42.8mg, and the yield is 93 percent.
FIG. 3 shows a hydrogen spectrum of the cis-1-styrylnaphthalene benzene as the target product obtained in example 4, and FIG. 4 shows a carbon spectrum of the cis-1-styrylnaphthalene benzene as the target product obtained in example 4, and it can be seen from FIGS. 3 and 4 that the structure of the product is correct.
Example 5
1- (3, 5-Dimethoxyphenylethynyl) benzene (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), NaOAc (0.40mmol,54.4mg), TEOA (0.75mmol,100L), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 140 ℃ for 32 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product was purified by column chromatography to give cis-1- (3, 5-dimethoxystyryl) benzene as a colorless liquid 43.2mg, 90% yield.
Example 6
Trimethyl (4-phenylethynylphenyl) silane (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), NaOAc (0.40mmol,54.4mg), TEOA (0.75mmol,100L), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 140 ℃ for 32 h.
After the reaction is finished, cooling to room temperature, adding 10mL of ethyl acetate, washing an organic phase for 3 times by using saturated saline solution, and using anhydrous Na for the organic phase2SO4Drying, and concentrating under reduced pressure. The crude product was purified by column chromatography to give cis-trimethyl (4-styrylphenyl) silane as a colorless liquid (48.9 mg, 97% yield).
FIG. 5 shows a hydrogen spectrum of the objective cis-trimethyl (4-styrylphenyl) silane obtained in example 6, and FIG. 6 shows a carbon spectrum of the objective cis-trimethyl (4-styrylphenyl) silane obtained in example 6, which shows that the structure of the objective cis-trimethyl (4-styrylphenyl) silane is correct in FIGS. 5 and 6.
Example 7
3-Phenylethynylpyridine 1(0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), NaOAc (0.40mmol,54.4mg), TEOA (0.75mmol,100L), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 140 ℃ for 32 h.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na 2SO4Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain cis-3-styrene pyridine, and the colorless liquid is 33.7mg, and the yield is 93 percent.
Example 8
1- (4-Propylphenylethynyl) -4-methoxybenzene (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), NaOAc (0.40mmol,54.4mg), TEOA (0.75mmol,100L), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 140 ℃ for 32 h.
After the reaction is finished, cooling to room temperature, adding 10mL of ethyl acetate, washing an organic phase for 3 times by using saturated saline solution, and using anhydrous Na for the organic phase2SO4Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain cis-1- (4-propylphenylethynyl) -4-methoxybenzene, 46.9mg of colorless liquid, and the yield is 93%.
Fig. 7 shows a hydrogen spectrum of the target product cis-1- (4-propylphenylethynyl) -4-methoxybenzene obtained in example 8, and fig. 8 shows a carbon spectrum of the target product cis-1- (4-propylphenylethynyl) -4-methoxybenzene obtained in example 8, and it can be seen from fig. 7 and 8 that the structure of the product is correct.
The invention also provides a method for selectively synthesizing trans-olefin by catalyzing semi-reduction of alkyne with palladium under hydrogen supply of alcohol, which comprises the following steps: ligand R, R-DIPAMP, a catalyst, alcohol and alkyne are subjected to alkyne reduction reaction in an organic solvent to generate trans-olefin;
The reduction reaction formula is:
the alkyne has a structural general formula as follows:
the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 120-150 ℃, and the time of the reduction reaction is 20-48 h;
the using amount of the catalyst is 5-20% of the molar using amount of alkyne; the dosage of the R, R-DIPAMP is 0.5-5 times of the molar dosage of alkyne, the dosage of the NaOAc is 0.5-5 times of the molar dosage of alkyne, the dosage of the TEOA is 0.5-5 times of the molar dosage of alkyne, and the dosage of the alcohol is 10-100 times of the molar dosage of alkyne;
wherein the organic solvent is acetonitrile;
the catalyst is selected from Pd (OAc)2、PdCl2Pd/C and PdCl2(PPh3)2At least one of (a).
Preferably, the catalyst is Pd (OAc)2The using amount is 10 percent of the molar using amount of alkyne;
the dosage of the NaOAc is 2 times of the molar dosage of alkyne, and the dosage of the TEOA is 2.5 times of the molar dosage of alkyne;
the alcohol is 95% ethanol, and the dosage of the alcohol is 50 times of the molar dosage of alkyne;
the temperature of the reduction reaction is 145 ℃, and the reaction time is 32-40 h.
Wherein, in the structural general formula of the alkyne, R and R' are selected from any one of the following groups: alkyl, benzene, naphthalene, pyridyl, alkylbenzene, alkoxybenzene, halobenzene and silyl benzene.
The following examples are provided to further illustrate the selective synthesis of trans-olefins by palladium-on-hydrogen catalysis of alkynes by hydrogen-donating alcohols.
Example 9
A15 ml pressure resistant tube was charged with tolane (0.20mmol), Pd (OAc)2(0.02mmol,448mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 145 ℃ for 36 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain the trans-stilbene, the white solid is 32.4mg, and the yield is 90%.
Fig. 9 shows a hydrogen spectrum of the target product trans-stilbene obtained in example 9, and fig. 10 shows a carbon spectrum of the target product trans-stilbene obtained in example 9, and it can be seen from fig. 9 and 10 that the structure of the product is correct.
Example 10
1- (4-Propylphenylethynyl) -4-methoxybenzene (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), the reaction was stirred at 145 ℃ for 36 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na 2SO4Drying, and concentrating under reduced pressure. The crude product was isolated and purified by column chromatography to give trans-1- (4-propylstyryl) -4-methoxybenzene as a white solid in an amount of 45.4mg in 90% yield.
Example 11
1- (3, 5-Dimethoxyphenylethynyl) benzene (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 145 ℃ for 36 hours.
After the reaction is finished, cooling to room temperature, adding 10mL of ethyl acetate, washing an organic phase for 3 times by using saturated saline solution, and using anhydrous Na for the organic phase2SO4Drying, and concentrating under reduced pressure. The crude product was purified by column chromatography to give trans-1- (3, 5-dimethoxystyryl) benzene as a white solid (44.6 mg, 93% yield).
Example 12
1- (4-chlorophenylacetylene) was added to a 15ml pressure-resistant tubeYl) -4-methylbenzene (0.20mmol), Pd (OAc)2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), the reaction was stirred at 145 ℃ for 36 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product was purified by column chromatography to give trans-1- (4-chlorostyryl) -4-methylbenzene as a white solid (34.2 mg, 75% yield).
Fig. 11 is a hydrogen spectrum and fig. 12 is a carbon spectrum of trans-stilbene as the target compound in example 12. as can be seen from fig. 11 and 12, the structure of trans-stilbene as the target compound in example 12 is correct.
Example 13
1-Acetylenphenyl-3, 5-bis (trifluoromethyl) benzene (0.20mmol), Pd (OAc) was put into a 15ml pressure resistant tube2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 145 ℃ for 36 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product was purified by column chromatography to give trans-1-vinylphenyl-3, 5-bis (trifluoromethyl) benzene as a white solid 54.5mg in 86% yield.
Example 14
To a 15ml pressure resistant tube was added trimethyl (4-ethynylphenyl) silane (0.20mmol), Pd (OAc)2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), the reaction was stirred at 145 ℃ for 36 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product was purified by column chromatography to give trans-trimethyl (4-vinylphenyl) silane as a white solid in an amount of 43.3mg, yield 86%.
Example 15
3-Phenylethynylpyridine (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 145 ℃ for 36 hours.
After the reaction is finished, cooling to room temperature, adding 10mL of ethyl acetate, washing an organic phase for 3 times by using saturated saline solution, and using anhydrous Na for the organic phase2SO4Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain trans-3-styrylpyridine as a white solid, 23.9mg and 81 percent of yield.
Fig. 13 shows a hydrogen spectrum of the target product trans-3-styrylpyridine obtained in example 15, and fig. 14 shows a carbon spectrum of the target product trans-3-styrylpyridine obtained in example 15, and it can be seen from fig. 13 and 14 that the structure of the product is correct.
Example 16
1-phenyl-1-propyne (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 145 ℃ for 36 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product was separated and purified by column chromatography to give trans-1-phenyl-1-propynylene as a colorless liquid in an amount of 19.1mg, in a yield of 81%.
Example 17
Methyl phenylpropionate (0.20mmol), Pd (OAc) was put in a 15ml pressure resistant tube2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 145 ℃ for 36 hours.
After the reaction was completed, the reaction mixture was cooled to room temperature, and 10mL of ethyl acetate was added. Washing the organic phase with saturated saline solution for 3 times, and washing the organic phase with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain trans-methyl phenylacrylate, 25.2mg of colorless liquid and 82% of yield.
Fig. 15 shows a hydrogen spectrum of the target product of trans-methyl phenylacrylate obtained in example 17, and fig. 16 shows a carbon spectrum of the target product of trans-methyl phenylacrylate obtained in example 17, and it can be seen from fig. 15 and 16 that the structure of the product is correct.
Example 18
5-decyne (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), the reaction was stirred at 145 ℃ for 36 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain the trans-5-decene, and the colorless liquid is 22.4mg, and the yield is 80 percent.
The invention also provides a method for reducing terminal alkyne into olefin by palladium catalysis in the presence of hydrogen supplied by alcohol, which comprises the following steps:
under the protection of inert gas, TEOA, NaOAc, a catalyst, alcohol and alkyne are subjected to alkyne reduction reaction in an organic solvent to generate cis-form alkene;
the reaction formula is as follows:
the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 60-100 ℃, and the reaction time is 20-30 h;
the using amount of the catalyst is 5-20% of the molar using amount of alkyne, the using amount of the NaOAc is 0.5-5 times of the molar using amount of alkyne, the using amount of the TEOA is 0.5-5 times of the molar using amount of alkyne, and the using amount of the alcohol is 10-100 times of the molar using amount of alkyne;
the organic solvent is acetonitrile;
the catalyst is selected from Pd (OAc)2、PdCl2Pd/C and PdCl2(PPh3)2At least one of (a).
Preferably, theThe catalyst is Pd (OAc)2The using amount is 10 percent of the molar using amount of alkyne;
the dosage of the NaOAc is 2 times of the molar dosage of alkyne, and the dosage of the TEOA is 2.5 times of the molar dosage of alkyne;
the alcohol is 95% ethanol, and the dosage of the alcohol is 50 times of the molar dosage of alkyne;
the temperature of the reduction reaction is 140 ℃, and the reaction time is 24 h.
Wherein, in the structural general formula of the alkyne, R is selected from any one of the following groups: alkyl, benzene, naphthalene, pyridyl, alkylbenzene, alkoxybenzene, halobenzene and silyl benzene.
Preferably, the environment of the reduction reaction is under the protection of nitrogen.
The palladium-catalyzed reduction of the terminal alkynes to alkenes with hydrogen donor from the alcohols is further illustrated below with reference to specific examples.
Example 19
N2Phenylacetylene (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube under protection2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 80 ℃ for 24 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain the trans-stilbene, colorless liquid 8.5mg, and the yield is 41%.
Fig. 17 shows a hydrogen spectrum of styrene, which is the target product obtained in example 19, and fig. 18 shows a carbon spectrum of styrene, which is the target product obtained in example 19, and it can be seen from fig. 17 and 18 that the structure of the product is correct.
Example 20
N2Under protection, 4-chlorophenylacetylene (0.20mmol), Pd (OAc) was added to a 15ml pressure-resistant tube2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), the reaction was stirred at 80 ℃ for 24 hours.
After the reaction is finished, cooling to the roomWarm, add 10mL ethyl acetate, wash the organic phase 3 times with saturated brine, and dry the organic phase with anhydrous Na 2SO4Drying, and concentrating under reduced pressure. The crude product was purified by column chromatography to give 4-chlorostyrene in 22.1mg as a colorless liquid in 80% yield.
Example 21
N2Under protection, 4-tert-butylacetylene (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 80 ℃ for 24 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na2SO4Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain the 4-tert-butyl styrene, colorless liquid 18.2mg, and the yield is 57 percent.
FIG. 19 shows a hydrogen spectrum of the objective 4-t-butylstyrene obtained in example 21, and FIG. 20 shows a carbon spectrum of the objective 4-t-butylstyrene obtained in example 21, and it can be seen from FIGS. 19 and 20 that the structure of the product is correct.
Example 22
N2Under protection, 4-nitrophenylacetylene (0.20mmol), Pd (OAc) was added to a 15ml pressure tube2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), the reaction was stirred at 80 ℃ for 24 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na 2SO4Drying, and concentrating under reduced pressure. The crude product was purified by column chromatography to give 4-nitrostyrene in a colorless liquid (17.3 mg, 58% yield).
FIG. 21 shows a hydrogen spectrum of the objective 4-nitrostyrene obtained in example 22, and FIG. 22 shows a carbon spectrum of the objective 4-nitrostyrene obtained in example 22, and it can be seen from FIGS. 21 and 22 that the structure of the product is correct.
Example 23
N2Under the protection of the air conditioner, the air conditioner is protected,3-ethynylpyridine (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), stirred at 80 ℃ for 24 hours.
After the reaction is finished, cooling to room temperature, adding 10mL of ethyl acetate, washing an organic phase for 3 times by using saturated saline solution, and using anhydrous Na for the organic phase2SO4Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain 3-vinylpyridine, 15.8mg of colorless liquid and 75 percent of yield.
Example 24
N2Under protection, 4-ethynylbiphenyl (0.20mmol), Pd (OAc) was added to a 15ml pressure resistant tube2(0.02mmol,4.48mg), R, R-DIPAMP (0.2mmol,18.32mg), 95% EtOH (10mmol,595L) and CH3CN (1.5mL), the reaction was stirred at 80 ℃ for 24 hours.
After the reaction, the mixture was cooled to room temperature, 10mL of ethyl acetate was added, the organic phase was washed with saturated brine 3 times, and the organic phase was washed with anhydrous Na 2SO4Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain 4-vinyl biphenyl, 15.8mg of colorless liquid, and the yield is 75 percent.
Fig. 23 shows a hydrogen spectrum of the objective 4-vinylbiphenyl obtained in example 24, and fig. 24 shows a carbon spectrum of the objective 4-vinylbiphenyl obtained in example 24, which shows that the structure of the product is correct in fig. 23 and 24.
While the foregoing is directed to the preferred embodiment of the present invention, it will be appreciated by those skilled in the art that various changes and modifications may be made therein without departing from the principles of the invention as set forth in the appended claims.
Claims (6)
1. A method for selectively synthesizing cis-olefin by catalyzing alkyne semi-reduction through palladium hydrogen donor alcohol is characterized by comprising the following steps:
TEOA, NaOAc, a catalyst, alcohol and alkyne are subjected to reduction reaction of alkyne in an organic solvent to generate cis-form alkene;
the reduction reaction formula is:
the alkyne has a structural general formula as follows:
the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 120-150 ℃, and the time of the reduction reaction is 20-48 h; the using amount of the catalyst is 5-20% of the molar using amount of alkyne, the using amount of the NaOAc is 0.5-5 times of the molar using amount of alkyne, the using amount of the TEOA is 0.5-5 times of the molar using amount of alkyne, and the using amount of the alcohol is 10-100 times of the molar using amount of alkyne;
Wherein the organic solvent is acetonitrile;
the catalyst is selected from Pd (OAc)2、PdCl2And PdCl2(PPh3)2At least one of (a);
in the structural general formula of the alkyne, R and R' are selected from any one of the following groups: phenyl, naphthyl, pyridyl, alkylphenyl, alkoxyphenyl, halophenyl, and silylphenyl.
2. The method for selectively synthesizing cis-alkene by semi-reducing alkyne under the catalysis of palladium hydrogen donor in alcohol according to claim 1, wherein the catalyst is Pd (OAc)2The using amount is 10 percent of the molar using amount of alkyne;
the dosage of the NaOAc is 2 times of the molar dosage of alkyne, and the dosage of the TEOA is 2.5 times of the molar dosage of alkyne; the alcohol is 95% ethanol, and the dosage of the alcohol is 50 times of the molar dosage of alkyne;
the temperature of the reduction reaction is 140 ℃, and the reaction time is 30-40 h.
3. A method for selectively synthesizing trans-olefin by catalyzing alkyne semi-reduction through palladium alcohol hydrogen supply is characterized by comprising the following steps: ligand R, R-DIPAMP, a catalyst, alcohol and alkyne are subjected to reduction reaction of alkyne in an organic solvent to generate trans-alkene; r and R' are selected from any one of the following groups: alkyl, phenyl, naphthyl, pyridyl, alkylphenyl, alkoxyphenyl, halophenyl and silylphenyl;
The reduction reaction formula is:
the alkyne has a structural general formula as follows:
the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 120-150 ℃, and the time of the reduction reaction is 20-48 h;
the dosage of the catalyst is 5-20% of the molar dosage of alkyne; the dosage of the R, R-DIPAMP is 0.5-5 times of the molar dosage of alkyne, and the dosage of the alcohol is 10-100 times of the molar dosage of alkyne;
wherein the organic solvent is acetonitrile;
the catalyst is selected from Pd (OAc)2、PdCl2Pd/C and PdCl2(PPh3)2At least one of (a).
4. The method for selective synthesis of trans-olefins by semi-reduction of alkynes with palladium-on-hydrogen catalysis according to claim 3, wherein the catalyst is Pd (OAc)2The using amount is 10 percent of the molar using amount of alkyne;
the alcohol is 95% ethanol, and the dosage of the alcohol is 50 times of the molar dosage of alkyne;
the temperature of the reduction reaction is 145 ℃, and the reaction time is 32-40 h.
5. A method for palladium-catalyzed reduction of terminal alkyne into olefin by alcohol hydrogen supply is characterized by comprising the following steps:
under the protection of nitrogen gas, performing alkyne reduction reaction on a ligand R, R-DIPAMP, a catalyst, alcohol and alkyne in an organic solvent to generate the alkene;
The reaction formula is as follows:
the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 60-100 ℃, and the reaction time is 20-30 h;
the dosage of the catalyst is 5-20% of the molar dosage of alkyne, and the dosage of the alcohol is 10-100 times of the molar dosage of alkyne;
the organic solvent is acetonitrile;
the catalyst is selected from Pd (OAc)2、PdCl2Pd/C and PdCl2(PPh3)2R is selected from any one of the following groups: alkyl, phenyl, naphthyl, pyridyl, alkylphenyl, alkoxyphenyl, halophenyl and silylphenyl.
6. The process of claim 5 wherein the catalyst is Pd (OAc)2The using amount is 10 percent of the molar using amount of alkyne;
the alcohol is 95% ethanol, and the dosage of the alcohol is 50 times of the molar dosage of alkyne; the temperature of the reduction reaction is 80 ℃, and the reaction time is 24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811607534.5A CN109776253B (en) | 2018-12-27 | 2018-12-27 | Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing semi-reduction of alkyne through palladium hydrogen donor by alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811607534.5A CN109776253B (en) | 2018-12-27 | 2018-12-27 | Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing semi-reduction of alkyne through palladium hydrogen donor by alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109776253A CN109776253A (en) | 2019-05-21 |
| CN109776253B true CN109776253B (en) | 2022-07-15 |
Family
ID=66497726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811607534.5A Active CN109776253B (en) | 2018-12-27 | 2018-12-27 | Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing semi-reduction of alkyne through palladium hydrogen donor by alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109776253B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218141A (en) * | 2019-06-20 | 2019-09-10 | 南通大学 | A kind of Photocatalysis selectivity synthesis Z- and E- olefins process |
| CN110256192A (en) * | 2019-06-25 | 2019-09-20 | 南通大学 | It is a kind of using alcohol be hydrogen source Photocatalysis selectivity synthesis cis and trans olefins process |
| CN112108175B (en) * | 2020-08-17 | 2021-11-19 | 西安交通大学 | Preparation method of aromatic olefin |
| CN112390830A (en) * | 2020-11-17 | 2021-02-23 | 江南大学 | Iridium catalyst for catalyzing rearrangement of propargyl ester to prepare substituted ketone compound |
| CN113443952B (en) * | 2021-07-15 | 2022-11-04 | 南通大学 | Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing alkyne semi-reduction through iridium with hydrogen supplied by water |
| CN113563150B (en) * | 2021-07-15 | 2022-09-02 | 南通大学 | Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing alkyne semi-reduction through palladium on hydrogen supplied by water |
-
2018
- 2018-12-27 CN CN201811607534.5A patent/CN109776253B/en active Active
Non-Patent Citations (4)
| Title |
|---|
| "Cobalt catalyzed stereodivergent semi-hydrogenation of alkynes using H 2 O as the hydrogen source";Kangkui Li;《ChemComm》;20190417;第55卷;第5663-5666页 * |
| "Controlled hydrogenation of diphenylacetylene using alkylammonium formate";Hideyuki Suzuki等;《Tetrahedron Letters》;20170824;第58卷;第3834–3837页 * |
| "Selective reduction of alkynes catalyzed by palladium acetate with sodium methoxide as the hydride source";Li-Lan Wei等;《Tetrahedron Letters》;20031231;第44卷;第1979-1981页 * |
| Jian-Ji Zhong等."Combining visible light catalysis and transfer hydrogenation for in situ efficient and selective semihydrogenation of alkynes under ambient conditions".《ChemComm》.2016,第52卷第1800-1803页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109776253A (en) | 2019-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109776253B (en) | Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing semi-reduction of alkyne through palladium hydrogen donor by alcohol | |
| Stork et al. | Regiospecific trapping of radicals from cyclization reactions. Cyclic nitriles via isocyanide trapping | |
| Jhingan et al. | Homogeneous catalysis with a heterogeneous palladium catalyst. An effective method for the cyclotrimerization of alkynes | |
| CN107721833B (en) | Method for preparing menthone | |
| Szudkowska-Frątczak et al. | Silylative coupling of olefins with vinylsilanes in the synthesis of functionalized alkenes | |
| Corre et al. | Regioselective hydrosilylation of terminal alkynes using pentamethylcyclopentadienyl iridium (III) metallacycle catalysts | |
| Kuninobu et al. | Development of Novel and Highly Efficient Methods to Construct Carbon–Carbon Bonds Using Group 7 Transition-Metal Catalysts | |
| Clavier et al. | [2+ 1] Cycloaddition Affording Methylene‐and Vinylidenecyclopropane Derivatives: A Journey around the Reactivity of Metal‐Phosphinito–Phosphinous Acid Complexes | |
| Zhang et al. | Efficient and environmentally friendly Glaser coupling of terminal alkynes catalyzed by multinuclear copper complexes under base-free conditions | |
| Narula et al. | Palladium-catalyzed cyclizations of bromo dienes | |
| Kadikova et al. | 2-Zincoethylzincation of 2-alkynylamines and 1-alkynylphosphines catalyzed by titanium (IV) isopropoxide and ethylmagnesium bromide | |
| Kozell et al. | A stereoselective organic base-catalyzed protocol for hydroamination of alkynes under solvent-free conditions | |
| CN113443952B (en) | Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing alkyne semi-reduction through iridium with hydrogen supplied by water | |
| CN109651115A (en) | A method of preparing L- menthones | |
| Benkeser et al. | A new reducing system: calcium metal in amines. Reduction of aromatic hydrocarbons | |
| Mirza-Aghayan et al. | Efficient method for the reduction of carbonyl compounds by triethylsilane catalyzed by PdCl2 | |
| CN105622560A (en) | Preparation method of theta-lactone | |
| CN113563150B (en) | Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing alkyne semi-reduction through palladium on hydrogen supplied by water | |
| Murtinho et al. | Novel tridentate ligands derived from (+)-camphoric acid for enantioselective ethylation of aromatic aldehydes | |
| Urbala | Solvent-free [Ru]-catalyzed isomerization of allyl glycidyl ether: The scope, effectiveness and recycling of catalysts, and exothermal effect | |
| CN107721858B (en) | Method for catalyzing asymmetric alpha-benzoylation of beta-keto ester by phase transfer | |
| Onishi et al. | Chemical reactivities of coordinatively unsaturated hydridotris (phosphonite)-cobalt (I) species photogenerated towards allylic and related compounds. | |
| CN113024340B (en) | Method for reducing alkyne into olefin by using nickel catalytic water as hydrogen source | |
| Silarska et al. | Efficient functionalization of olefins by arylsilanes catalyzed by palladium anionic complexes | |
| Blum et al. | Transfer hydrogenation of diarylacetylenes by polymethylhydrosiloxane in the presence of the RhCl3-Aliquat 336 catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Sun Fei Inventor after: Wang Chengniu Inventor after: Yang Jinfei Inventor after: Wu Xiaolong Inventor after: Wang Guishuan Inventor after: Gong Shengnan Inventor before: Wang Chengniu Inventor before: Sun Fei Inventor before: Yang Jinfei Inventor before: Wu Xiaolong Inventor before: Wang Guishuan Inventor before: Gong Shengnan |
|
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Chengniu Inventor after: Sun Fei Inventor after: Yang Jinfei Inventor after: Wu Xiaolong Inventor after: Wang Guishuan Inventor after: Gong Shengnan Inventor before: Sun Fei Inventor before: Wang Chengniu Inventor before: Yang Jinfei Inventor before: Wu Xiaolong Inventor before: Wang Guishuan Inventor before: Gong Shengnan |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |