CN109776253A - Alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis is suitable, trans olefins methods - Google Patents
Alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis is suitable, trans olefins methods Download PDFInfo
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Abstract
A kind of suitable, trans olefins methods that the present invention provides alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis, include the following steps: the reduction reaction that TEOA, NaOAc, catalyst, alcohol and alkynes are carried out to alkynes in organic solvent, and reaction generates cis-form olefin；Ligand, catalyst, alcohol and alkynes are carried out to the reduction reaction of alkynes in organic solvent, reaction generates trans olefins；The reactor of reduction reaction is the voltage-resistant reactor of sealing, and the temperature of reduction reaction is 120~150 DEG C, and the time of reduction reaction is 20~48h；The dosage of catalyst is the 5~20% of alkynes mole dosage, and the dosage of alcohol is 10~100 times of alkynes mole dosage；The dosage of R, R-DIPAMP are 0.5~5 times of alkynes mole dosage.In the present invention, catalyst system has high chemical reaction and stereoselectivity, can high yield synthesizing cis or trans olefins product；Catalyst system is strong to the universality of substrate, and the alkynes containing various functional groups can efficiently carry out reduction reaction with high selectivity.
Description
Technical field
The invention belongs to fine chemical product catalytic synthetic techniques fields, and in particular to a kind of alcohol hydrogen supply palladium chtalyst alkynes half
Restore that selectivity synthesis is suitable, methods of trans olefins.
Background technique
Conjugated alkene compound is the important intermediate of the synthesis such as drug, photoelectric material, 1,2- diphenylethylene compounds
It is wherein very important a kind of compound.As much having various bioactivity (antitumor, antiangiogenic, cytotoxin
Property and prevent hyperplasia etc.) compound of the structural unit of talan containing 1,2- is isolated from natural products.Such as
Cis-structure Combretastatin (combretastatin) A-4 is a kind of good antineoplastic, it is possible to become microtubulin-resisting
First marketed drug in polymeric drug.The resveratrol Resveratrol of transconfiguration has extraordinary anti-oxidantization
Close object.In addition, there are also the phenelzine sulfates with antidepressant effect obtained using the styrene of end group as Material synthesis
Phenelzine Sulfate Salt。
The reduction reaction synthetic method of alkynes mainly has: hydrogen hydrogen supply, formic acid hydrogen supply, ammonia borine hydrogen supply direct-reduction process.
The Lindlar of nineteen fifty-two Germany uses catalyst Pd-CaCO for the first time3- PbO and Pd-BaS2O4It is two kinds of quinoline, hydrogen catalyzed by alkynes
It is selectively reduced to cis-form olefin, such method is widely used in synthesis chemistry, but there are following three for the method
A problem: (1) preparation method of Lindlar catalyst determines the catalytic activity of catalyst, uses the reduction of Lindlar catalyst
The reaction that the usual mistake reduction reaction that not can avoid alkynes of reaction, i.e. alkynes are reduced to saturated alkane, leads to the choosing of reduction reaction
Selecting property (selectivity of chemical equation) is undesirable, and becomes difficult product separation and purifying；(2) reduction reaction uses traditional hydrogen
Gas is needing special requirement using reactor and secure context as hydrogen source；(3) this method can not obtain trans olefins.
Therefore realizing that selectively reducing alkyne is the research of alkene with non-hydrogen hydrogen source is always the hot spot and again of synthesis chemical field
Want one of research contents.2016, Kenan Tokmic passed through synthesis (MesCCC) Co (N2)(PPh3) catalyst, in hydrogen item
Under part, alkynes restores to obtain cis-form olefin, and this method equally exists three problems above.
Later, 2008, Elsevier used formic acid as hydrogen source, used NHC (N heterocycle carbine) as ligand to stablize Pd
(0) alkynes is reduced to cis-form olefin reaction to realize by catalyst.The chemical reaction and stereoselectivity are high, to without miscellaneous
The alkynes yield of atom is higher, and reaction condition is relatively mild.The disadvantage is that the selection to some substrates (such as 1,3 diines, alkynes ester etc.)
Property and yield are undesirable, it is more difficult to obtain trans olefins, while formic acid is more expensive, especially ligand NHC is very expensive, limits its big rule
Mould uses.Alami et al. is reported with silane Et3Two aryne hydrocarbon are highly selectively reduced to by SiH as hydrogen source, by two-step method
Cis- two fragrant alkene, process is in PtO2In the presence of catalyst, the addition product of hydrogen silane and two aryne is firstly generated, then
The desiliconization alkyl that flows back in the presence of TBAF (tetrabutylammonium) of equivalent obtains cis- two fragrant alkene.Although the choosing of the reaction system
Selecting property is very high, but due to keep the yield of final alkene undesirable through two-step reaction, and has used the TBAF of equivalent as phase
Transfer catalyst is equally difficult to obtain trans olefins, and reaction system is made to lack practicability.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis is suitable, anti-
The method of formula alkene, catalyst is cheap, is easy to get, and operation is simple, is suitable for being mass produced；Using cheap ethyl alcohol as hydrogen
Source, safety economy are environmentally protective；Catalyst system has high chemical reaction and stereoselectivity, and energy high yield synthesis is suitable
Formula or trans olefins product；Catalyst system is strong to the universality of substrate, and the alkynes containing various functional groups can be carried out efficiently
Reduction reaction with high selectivity.
In order to solve the above technical problems, the embodiment of the present invention provides a kind of alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity
The method of synthesizing cis alkene, includes the following steps:
TEOA, NaOAc, catalyst, alcohol and alkynes are carried out to the reduction reaction of alkynes in organic solvent, reaction generates suitable
Formula alkene；
Reduction reaction formula are as follows:
The general structure of the alkynes are as follows:
The reactor of reduction reaction is the voltage-resistant reactor of sealing, and the temperature of reduction reaction is 120~150 DEG C, and reduction is anti-
The time answered is 20~48h；
The dosage of the catalyst is the 5~20% of alkynes mole dosage, and the dosage of the NaOAc is alkynes mole dosage
0.5~5 times, the dosage of the TEOA is 0.5~5 times of alkynes mole dosage, and the dosage of the alcohol is alkynes mole dosage
10~100 times；
Wherein, the organic solvent is acetonitrile；
The catalyst is selected from Pd (OAc)2、PdCl2, Pd/C and PdCl2(PPh3)2At least one of.
Preferably, the catalyst selects Pd (OAc)2, dosage is the 10% of alkynes mole dosage；
The dosage of the NaOAc is 2 times of alkynes mole dosage, and the dosage of the TEOA is the 2.5 of alkynes mole dosage
Times；
The alcohol is 95% ethyl alcohol, and dosage is 50 times of alkynes mole dosage.
Preferably, the temperature of reduction reaction is 140 DEG C, and the reaction time is 30~40h.
Wherein, in the general structure of the alkynes, any one of R and R' in following each genes: alkyl, phenyl ring,
Naphthalene nucleus, pyridyl group, alkylbenzene, alkoxy benzene, halogeno-benzene and silylation benzene.
The present invention also provides a kind of methods of alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis trans olefins, including such as
Lower step: by ligand R, R-DIPAMP, catalyst, alcohol and alkynes carry out the reduction reaction of alkynes, reaction life in organic solvent
At trans olefins；
Reduction reaction formula are as follows:
The general structure of the alkynes are as follows:
The reactor of reduction reaction is the voltage-resistant reactor of sealing, and the temperature of reduction reaction is 120~150 DEG C, and reduction is anti-
The time answered is 20~48h；
The dosage of the catalyst is the 5~20% of alkynes mole dosage；The dosage of the R, R-DIPAMP are rubbed for alkynes
0.5~5 times of that dosage, the dosage of the NaOAc are 0.5~5 times of alkynes mole dosage, and the dosage of the TEOA is alkynes
0.5~5 times of mole dosage, the dosage of the alcohol are 10~100 times of alkynes mole dosage；
Wherein, the organic solvent is acetonitrile；
The catalyst is selected from Pd (OAc)2、PdCl2, Pd/C and PdCl2(PPh3)2At least one of.
Preferably, the catalyst selects Pd (OAc)2, dosage is the 10% of alkynes mole dosage；
The dosage of the NaOAc is 2 times of alkynes mole dosage, and the dosage of the TEOA is the 2.5 of alkynes mole dosage
Times；
The alcohol is 95% ethyl alcohol, and dosage is 50 times of alkynes mole dosage.
Preferably, the temperature of reduction reaction is 145 DEG C, and the reaction time is 32~40h.
Wherein, in the general structure of the alkynes, any one of R and R' in following each groups: alkyl, phenyl ring,
Naphthalene nucleus, pyridyl group, alkylbenzene, alkoxy benzene, halogeno-benzene and silylation benzene.
The present invention also provides the methods that a kind of alcohol hydrogen supply palladium chtalyst reduction terminal alkyne is alkene, include the following steps:
Under nitrogen (anaerobic) protection, TEOA, NaOAc, catalyst, alcohol and alkynes are subjected to alkynes in organic solvent
Reduction reaction, reaction generate the cis-form olefin；
Reaction equation are as follows:
；
The reactor of reduction reaction is the voltage-resistant reactor of sealing, and the temperature of reduction reaction is 60~100 DEG C, the reaction time
For 20~30h；
The dosage of the catalyst is the 5~20% of alkynes mole dosage, and the dosage of the NaOAc is alkynes mole dosage
0.5~5 times, the dosage of the TEOA is 0.5~5 times of alkynes mole dosage, and the dosage of the alcohol is alkynes mole dosage
10~100 times；
The organic solvent is acetonitrile；
The catalyst is selected from Pd (OAc)2、PdCl2And PdCl2(PPh3)2At least one of.
Preferably, the catalyst selects Pd (OAc)2, dosage is the 10% of alkynes mole dosage；
The dosage of the NaOAc is 2 times of alkynes mole dosage, and the dosage of the TEOA is the 2.5 of alkynes mole dosage
Times；
The alcohol is 95% ethyl alcohol, and dosage is 50 times of alkynes mole dosage.
Preferably, the temperature of reduction reaction is 140 DEG C, and the reaction time is for 24 hours.
Wherein, in the general structure of the alkynes, any one of R in following each groups: alkyl, phenyl ring, naphthalene nucleus,
Pyridyl group, alkylbenzene, alkoxy benzene, halogeno-benzene and silylation benzene.
Preferably, the environment of reduction reaction is under nitrogen protection.
The advantageous effects of the above technical solutions of the present invention are as follows:
The innovation of the invention consists in that: (1) use alcohol as hydrogen source, it is cheap and easy to get, it is safe and efficient, it is economic and environment-friendly；It (2) can be with
Cis-form olefin and trans olefins are obtained to efficient selective, equally applies to terminal alkyne and synthesizes to obtain end group alkene.
Reducing alkyne provided by the invention is the method for alkene, is had the following characteristics that
(1) catalyst is cheap and easy to get, and operation is simple, is suitable for being mass produced；
(2) using cheap ethyl alcohol as hydrogen source, safety economy is environmentally protective；
(3) catalyst system has high chemical reaction and stereoselectivity, can high yield synthesizing cis or trans-
Olefin product；
(4) catalyst system is strong to the universality of substrate, and the alkynes containing various functional groups can efficiently carry out highly selective
Ground reduction reaction.
Detailed description of the invention
Fig. 1 be 1 gained target product of the embodiment of the present invention it is cis--the hydrogen spectrogram of talan；
Fig. 2 be 1 gained target product of the embodiment of the present invention it is cis--the difference carbon spectrogram of talan；
Fig. 3 is the hydrogen spectrogram of the cis- -1- styryl naphthalene benzene of 4 gained target product of the embodiment of the present invention；
Fig. 4 is the carbon spectrogram of the cis- -1- styryl naphthalene benzene of 4 gained target product of the embodiment of the present invention；
Fig. 5 be 6 gained target product of the embodiment of the present invention it is cis--hydrogen of trimethyl (4- styryl phenyl) silane spectrum
Figure；
Fig. 6 be 6 gained target product of the embodiment of the present invention it is cis--carbon of trimethyl (4- styryl phenyl) silane spectrum
Figure；
Fig. 7 is the hydrogen of the 8 cis- -1- of gained target product of the embodiment of the present invention (4- propyl phenylacetylene base) -4- methoxybenzene
Spectrogram；
Fig. 8 is the carbon of the 8 cis- -1- of gained target product of the embodiment of the present invention (4- propyl phenylacetylene base) -4- methoxybenzene
Spectrogram；
Fig. 9 be 9 gained target product of the embodiment of the present invention it is trans--the hydrogen spectrogram of talan；
Figure 10 be 9 gained target product of the embodiment of the present invention it is trans--the carbon spectrogram of talan；
Figure 11 be 12 gained target product of the embodiment of the present invention it is trans--the hydrogen spectrogram of talan；
Figure 12 be 12 gained target product of the embodiment of the present invention it is trans--the carbon spectrogram of talan；
Figure 13 is the hydrogen spectrogram of the trans- -3- stibazole of 15 gained target product of the embodiment of the present invention；
Figure 14 is the carbon spectrogram of the trans- -3- stibazole of 15 gained target product of the embodiment of the present invention；
Figure 15 be 17 gained target product of the embodiment of the present invention it is trans--the hydrogen spectrogram of cinnamic acid methyl esters；
Figure 16 be 17 gained target product of the embodiment of the present invention it is trans--the carbon spectrogram of cinnamic acid methyl esters；
Figure 17 is the hydrogen spectrogram of 19 gained target product styrene of the embodiment of the present invention；
Figure 18 is the carbon spectrogram of 19 gained target product styrene of the embodiment of the present invention；
Figure 19 is the hydrogen spectrogram of 21 gained target product 4- t-butyl styrene of the embodiment of the present invention；
Figure 20 is the carbon spectrogram of 21 gained target product 4- t-butyl styrene of the embodiment of the present invention；
Figure 21 is the hydrogen spectrogram of 22 gained target product 4- nitrostyrolene of the embodiment of the present invention；
Figure 22 is the carbon spectrogram of 22 gained target product 4- nitrostyrolene of the embodiment of the present invention；
Figure 23 is the hydrogen spectrogram of 24 gained target product 4- vinyl biphenyl of the embodiment of the present invention；
Figure 24 is the carbon spectrogram of 24 gained target product 4- vinyl biphenyl of the embodiment of the present invention.
Specific embodiment
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with attached drawing and tool
Body embodiment is described in detail.
The present invention provides a kind of methods of alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis cis-form olefin, including such as
Lower step:
TEOA, NaOAc, catalyst, alcohol and alkynes are carried out to the reduction reaction of alkynes in organic solvent, reaction generates suitable
Formula alkene；
Reduction reaction formula are as follows:
The general structure of the alkynes are as follows:
The reactor of reduction reaction is the voltage-resistant reactor of sealing, and the temperature of reduction reaction is 120~150 DEG C, and reduction is anti-
The time answered is 20~48h；
The dosage of the catalyst is the 5~20% of alkynes mole dosage, and the dosage of the NaOAc is alkynes mole dosage
0.5~5 times, the dosage of the TEOA is 0.5~5 times of alkynes mole dosage, and the dosage of the alcohol is alkynes mole dosage
10~100 times；
Wherein, the organic solvent is acetonitrile；
The catalyst is selected from Pd (OAc)2、PdCl2, Pd/C and PdCl2(PPh3)2At least one of.
Preferably, the catalyst selects Pd (OAc)2, dosage is the 10% of alkynes mole dosage；
The dosage of the NaOAc is 2 times of alkynes mole dosage, and the dosage of the TEOA is the 2.5 of alkynes mole dosage
Times；
The alcohol is 95% ethyl alcohol, and dosage is 50 times of alkynes mole dosage；
The temperature of reduction reaction is 140 DEG C, and the reaction time is 30~40h.
Wherein, in the general structure of the alkynes, any one of R and R' in following each genes: alkyl, phenyl ring,
Naphthalene nucleus, pyridyl group, alkylbenzene, alkoxy benzene, halogeno-benzene and silylation benzene.
Below with reference to specific embodiment, the cis- alkene of alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis is further described
The method of hydrocarbon.
Embodiment 1
Tolans (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol, 4.48mg), NaOAc
(0.40mmol, 54.4mg), TEOA (0.75mmol, 100L), 95%EtOH (10mmol, 595L) and CH3CN (1.5mL),
140 DEG C are stirred to react 32 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains cis--talan, colourless liquid
32.4mg, yield 90%.
Fig. 1 show the 1 gained target product of embodiment it is cis--the hydrogen spectrogram of talan, Fig. 2 show the embodiment
1 gained target product is cis--the difference carbon spectrogram of talan, by Fig. 1 and Fig. 2 it is found that the product structure is correct.
Embodiment 2
1- (3- chlorobenzene acetenyl) -3- methylbenzene (0.20mmol), Pd (OAc) are added in 15ml pressure pipe2
(0.02mmol, 4.48mg), NaOAc (0.40mmol, 54.4mg), TEOA (0.75mmol, 100L), 95%EtOH (10mmol,
595L) and CH3CN (1.5mL), 140 DEG C are stirred to react 32 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains cis- -1- (3- chlorostyrene base) -3- methyl
Benzene, colourless liquid 43.8mg, yield 96%.
Embodiment 3
1- (3- fluorophenylethynyl) -3,5- bis- (trifluoromethyl) benzene (0.20mmol), Pd are added in 15ml pressure pipe
(OAc)2(0.02mmol, 4.48mg), NaOAc (0.40mmol, 54.4mg), TEOA (0.75mmol, 100L), 95%EtOH
(10mmol, 595L) and CH3CN (1.5mL), 140 DEG C are stirred to react 32 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains cis- -1- (3- fluorostyryl) -3,5- two
(trifluoromethyl) benzene, colourless liquid 65.5mg, yield 98%.
Embodiment 4
1- phenylacetylene base naphthalene benzene (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol, 4.48mg),
NaOAc (0.40mmol, 54.4mg), TEOA (0.75mmol, 100L), 95%EtOH (10mmol, 595L) and CH3CN
(1.5mL), 140 DEG C are stirred to react 32 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains cis- -1- styryl naphthalene benzene, colourless liquid
42.8mg, yield 93%.
Fig. 3 show the hydrogen spectrogram of the cis- -1- styryl naphthalene benzene of 4 gained target product of embodiment, and Fig. 4 show this
The carbon spectrogram of the cis- -1- styryl naphthalene benzene of 4 gained target product of embodiment, as can be seen from figs. 3 and 4, the product structure is correct.
Embodiment 5
1- (3,5- dimethoxy phenylacetylene base) benzene (0.20mmol), Pd (OAc) are added in 15ml pressure pipe2
(0.02mmol, 4.48mg), NaOAc (0.40mmol, 54.4mg), TEOA (0.75mmol, 100L), 95%EtOH (10mmol,
595L) and CH3CN (1.5mL), 140 DEG C are stirred to react 32 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains cis- -1- (3,5- dimethoxy styrene
Base) benzene, colourless liquid 43.2mg, yield 90%.
Embodiment 6
Trimethyl (4- phenylacetylene base phenyl) silane (0.20mmol), Pd (OAc) are added in 15ml pressure pipe2
(0.02mmol, 4.48mg), NaOAc (0.40mmol, 54.4mg), TEOA (0.75mmol, 100L), 95%EtOH (10mmol,
595L) and CH3CN (1.5mL), 140 DEG C are stirred to react 32 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains cis--trimethyl (4- styryl phenyl)
Silane, colourless liquid 48.9mg, yield 97%.
Fig. 5 show the 6 gained target product of embodiment it is cis--hydrogen of trimethyl (4- styryl phenyl) silane spectrum
Figure, Fig. 6 show the 6 gained target product of embodiment it is cis--the carbon spectrogram of trimethyl (4- styryl phenyl) silane, by scheming
5 and Fig. 6 is it is found that the product structure is correct.
Embodiment 7
3- phenylacetylene pyridine 1 (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol, 4.48mg),
NaOAc (0.40mmol, 54.4mg), TEOA (0.75mmol, 100L), 95%EtOH (10mmol, 595L) and CH3CN
(1.5mL), 140 DEG C are stirred to react 32 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains cis- -3- styryl pyridine, colourless liquid
33.7mg, yield 93%.
Embodiment 8
1- (4- propyl phenylacetylene base) -4- methoxybenzene (0.20mmol), Pd (OAc) are added in 15ml pressure pipe2
(0.02mmol, 4.48mg), NaOAc (0.40mmol, 54.4mg), TEOA (0.75mmol, 100L), 95%EtOH (10mmol,
595L) and CH3CN (1.5mL), 140 DEG C are stirred to react 32 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains cis- -1- (4- propyl phenylacetylene base) -4- first
Oxygroup benzene, colourless liquid 46.9mg, yield 93%.
Fig. 7 show the hydrogen of the embodiment the 8 cis- -1- of gained target product (4- propyl phenylacetylene base) -4- methoxybenzene
Spectrogram, Fig. 8 show the carbon spectrum of the embodiment the 8 cis- -1- of gained target product (4- propyl phenylacetylene base) -4- methoxybenzene
Figure, by Fig. 7 and Fig. 8 it is found that the product structure is correct.
The present invention also provides a kind of methods of alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis trans olefins, including such as
Lower step: by ligand R, R-DIPAMP, catalyst, alcohol and alkynes carry out the reduction reaction of alkynes, reaction life in organic solvent
At trans olefins；
Reduction reaction formula are as follows:
The general structure of the alkynes are as follows:
The reactor of reduction reaction is the voltage-resistant reactor of sealing, and the temperature of reduction reaction is 120~150 DEG C, and reduction is anti-
The time answered is 20~48h；
The dosage of the catalyst is the 5~20% of alkynes mole dosage；The dosage of the R, R-DIPAMP are rubbed for alkynes
0.5~5 times of that dosage, the dosage of the NaOAc are 0.5~5 times of alkynes mole dosage, and the dosage of the TEOA is alkynes
0.5~5 times of mole dosage, the dosage of the alcohol are 10~100 times of alkynes mole dosage；
Wherein, the organic solvent is acetonitrile；
The catalyst is selected from Pd (OAc)2、PdCl2, Pd/C and PdCl2(PPh3)2At least one of.
Preferably, the catalyst selects Pd (OAc)2, dosage is the 10% of alkynes mole dosage；
The dosage of the NaOAc is 2 times of alkynes mole dosage, and the dosage of the TEOA is the 2.5 of alkynes mole dosage
Times；
The alcohol is 95% ethyl alcohol, and dosage is 50 times of alkynes mole dosage；
The temperature of reduction reaction is 145 DEG C, and the reaction time is 32~40h.
Wherein, in the general structure of the alkynes, any one of R and R' in following each groups: alkyl, phenyl ring,
Naphthalene nucleus, pyridyl group, alkylbenzene, alkoxy benzene, halogeno-benzene and silylation benzene.
Below with reference to specific embodiment, the trans- alkene of alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis is further described
The method of hydrocarbon.
Embodiment 9
Tolans (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol, 4.48mg), R, R-
DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN (1.5mL), 145 DEG C are stirred to react 36
Hour.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains trans--talan, white solid
32.4mg, yield 90%.
Fig. 9 show the 9 gained target product of embodiment it is trans--the hydrogen spectrogram of talan, Figure 10 show the implementation
9 gained target product of example is trans--the carbon spectrogram of talan, by Fig. 9, Figure 10 it is found that the product structure is correct.
Embodiment 10
1- (4- propyl phenylacetylene base) -4- methoxybenzene (0.20mmol), Pd (OAc) are added in 15ml pressure pipe2
(0.02mmol, 4.48mg), R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN
(1.5mL), 145 DEG C are stirred to react 36 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains anti-form-1-(4- propylstyrene base)-4- first
Oxygroup benzene, white solid 45.4mg, yield 90%.
Embodiment 11
1- (3,5- dimethoxy phenylacetylene base) benzene (0.20mmol), Pd (OAc) are added in 15ml pressure pipe2
(0.02mmol, 4.48mg), R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN
(1.5mL), 145 DEG C are stirred to react 36 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains anti-form-1-(3,5- dimethoxy styrene
Base) benzene, white solid 44.6mg, yield 93%.
Embodiment 12
1- (4- chlorobenzene acetenyl) -4- methylbenzene (0.20mmol), Pd (OAc) are added in 15ml pressure pipe2
(0.02mmol, 4.48mg), R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN
(1.5mL), 145 DEG C are stirred to react 36 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains anti-form-1-(4- chlorostyrene base)-4- methyl
Benzene, white solid 34.2mg, yield 75%.
Figure 11 be the 12 gained target product of embodiment it is trans--the hydrogen spectrogram of talan, Figure 12 is 12 institute of embodiment
Target product it is trans--the carbon spectrogram of talan, by Figure 11, Figure 12 it is found that the product structure is correct.
Embodiment 13
1- acetylene phenyl -3,5- bis- (trifluoromethyl) benzene (0.20mmol), Pd (OAc) are added in 15ml pressure pipe2
(0.02mmol, 4.48mg), R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN
(1.5mL), 145 DEG C are stirred to react 36 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains anti-form-1-two (trifluoro of vinyl phenyl-3,5-
Methyl) benzene, white solid 54.5mg, yield 86%.
Embodiment 14
Trimethyl (4- ethynyl phenyl) silane (0.20mmol), Pd (OAc) are added in 15ml pressure pipe2
(0.02mmol, 4.48mg), R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN
(1.5mL), 145 DEG C are stirred to react 36 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains trans--trimethyl (4- ethenylphenyl) silicon
Alkane, white solid 43.3mg, yield 86%.
Embodiment 15
3- phenylethynylpyridin (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol, 4.48mg),
R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN (1.5mL), 145 DEG C of stirrings are anti-
It answers 36 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains trans- -3- stibazole, white solid
23.9mg, yield 81%.
Figure 13 show the hydrogen spectrogram of the trans- -3- stibazole of 15 gained target product of embodiment,
Figure 14 show the carbon spectrogram of the trans- -3- stibazole of 15 gained target product of embodiment, by Figure 13, figure
14 it is found that the product structure is correct.
Embodiment 16
1- phenyl -1- propine (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol, 4.48mg),
R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN (1.5mL), 145 DEG C of stirrings are anti-
It answers 36 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains anti-form-1-phenyl-1- propine alkene, colourless liquid
Body 19.1mg, yield 81%.
Embodiment 17
Phenylpropiolic acid methyl esters (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol, 4.48mg), R,
R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN (1.5mL), 145 DEG C are stirred to react
36 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added.Organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains trans--cinnamic acid methyl esters, colourless liquid
25.2mg, yield 82%.
Figure 15 show the 17 gained target product of embodiment it is trans--the hydrogen spectrogram of cinnamic acid methyl esters, Figure 16 show
The 17 gained target product of embodiment is trans--the carbon spectrogram of cinnamic acid methyl esters, by Figure 15 and Figure 16 it is found that the product structure just
Really.
Embodiment 18
5- decine (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol, 4.48mg), R, R-
DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN (1.5mL), 145 DEG C are stirred to react 36
Hour.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains trans- -5- decene, colourless liquid 22.4mg,
Yield 80%.
The present invention also provides the methods that a kind of alcohol hydrogen supply palladium chtalyst reduction terminal alkyne is alkene, include the following steps:
Under inert gas protection, TEOA, NaOAc, catalyst, alcohol and alkynes are carried out to going back for alkynes in organic solvent
Original reaction, reaction generate the cis-form olefin；
Reaction equation are as follows:
The reactor of reduction reaction is the voltage-resistant reactor of sealing, and the temperature of reduction reaction is 60~100 DEG C, the reaction time
For 20~30h；
The dosage of the catalyst is the 5~20% of alkynes mole dosage, and the dosage of the NaOAc is alkynes mole dosage
0.5~5 times, the dosage of the TEOA is 0.5~5 times of alkynes mole dosage, and the dosage of the alcohol is alkynes mole dosage
10~100 times；
The organic solvent is acetonitrile；
The catalyst is selected from Pd (OAc)2、PdCl2, Pd/C and PdCl2(PPh3)2At least one of.
Preferably, the catalyst selects Pd (OAc)2, dosage is the 10% of alkynes mole dosage；
The dosage of the NaOAc is 2 times of alkynes mole dosage, and the dosage of the TEOA is the 2.5 of alkynes mole dosage
Times；
The alcohol is 95% ethyl alcohol, and dosage is 50 times of alkynes mole dosage；
The temperature of reduction reaction is 140 DEG C, and the reaction time is for 24 hours.
Wherein, in the general structure of the alkynes, any one of R in following each groups: alkyl, phenyl ring, naphthalene nucleus,
Pyridyl group, alkylbenzene, alkoxy benzene, halogeno-benzene and silylation benzene.
Preferably, the environment of reduction reaction is under nitrogen protection.
Combined with specific embodiments below, the method that alcohol hydrogen supply palladium chtalyst reduction terminal alkyne is alkene is further described.
Embodiment 19
N2Under protection, phenylacetylene (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol, 4.48mg),
R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN (1.5mL), 80 DEG C of stirrings are anti-
It answers 24 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains trans--talan, colourless liquid 8.5mg,
Yield 41%.
Figure 17 show the hydrogen spectrogram of the 19 gained target product styrene of embodiment, and Figure 18 show 19 institute of embodiment
The carbon spectrogram for obtaining target product styrene, by Figure 17, Figure 18 it is found that the product structure is correct.
Embodiment 20
N2Under protection, 4- chlorobenzene acetylene (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol,
4.48mg), R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN (1.5mL), 80
It DEG C is stirred to react 24 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains 4- chlorostyrene, and colourless liquid 22.1mg is produced
Rate 80%.
Embodiment 21
N2Under protection, 4- tert-butyl benzene acetylene (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol,
4.48mg), R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN (1.5mL), 80
It DEG C is stirred to react 24 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains 4- t-butyl styrene, colourless liquid
18.2mg, yield 57%.
Figure 19 show the hydrogen spectrogram of the 21 gained target product 4- t-butyl styrene of embodiment, and Figure 20 show the reality
The carbon spectrogram for applying 21 gained target product 4- t-butyl styrene of example, by Figure 19, Figure 20 it is found that the product structure is correct.
Embodiment 22
N2Under protection, 4- nitrobenzene acetylene (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol,
4.48mg), R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN (1.5mL), 80
It DEG C is stirred to react 24 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains 4- nitrostyrolene, colourless liquid 17.3mg,
Yield 58%.
Figure 21 show the hydrogen spectrogram of the 22 gained target product 4- nitrostyrolene of embodiment, and Figure 22 show the implementation
The carbon spectrogram of 22 gained target product 4- nitrostyrolene of example, by Figure 21, Figure 22 it is found that the product structure is correct.
Embodiment 23
N2Under protection, 3- ethynyl pyridine (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol,
4.48mg), R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN (1.5mL), 80
It DEG C is stirred to react 24 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains 3- vinylpyridine, colourless liquid 15.8mg,
Yield 75%.
Embodiment 24
N2Under protection, 4- acetenyl biphenyl (0.20mmol) is added in 15ml pressure pipe, Pd (OAc)2(0.02mmol,
4.48mg), R, R-DIPAMP (0.2mmol, 18.32mg), 95%EtOH (10mmol, 595L) and CH3CN (1.5mL), 80
It DEG C is stirred to react 24 hours.
End of reaction is cooled to room temperature, and ethyl acetate 10mL is added, and organic phase is with saturated common salt water washing 3 times, organic phase
Use anhydrous Na2SO4It is dry, it is concentrated under reduced pressure.Crude product column chromatographic isolation and purification obtains 4- vinyl biphenyl, colourless liquid 15.8mg,
Yield 75%.
Figure 23 show the hydrogen spectrogram of the 24 gained target product 4- vinyl biphenyl of embodiment, and Figure 24 show the implementation
The carbon spectrogram of 24 gained target product 4- vinyl biphenyl of example, by Figure 23, Figure 24 it is found that the product structure is correct.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of method of alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis cis-form olefin, which is characterized in that including as follows
Step:
TEOA, NaOAc, catalyst, alcohol and alkynes are carried out to the reduction reaction of alkynes in organic solvent, reaction generates cis- alkene
Hydrocarbon；
Reduction reaction formula are as follows:
The general structure of the alkynes are as follows:
The reactor of reduction reaction is the voltage-resistant reactor of sealing, and the temperature of reduction reaction is 120~150 DEG C, reduction reaction
Time is 20~48h；
The dosage of the catalyst is the 5~20% of alkynes mole dosage, and the dosage of the NaOAc is alkynes mole dosage
0.5~5 times, the dosage of the TEOA is 0.5~5 times of alkynes mole dosage, and the dosage of the alcohol is alkynes mole dosage
10~100 times；
Wherein, the organic solvent is acetonitrile；
The catalyst is selected from Pd (OAc)2、PdCl2And PdCl2(PPh3)2At least one of.
2. the method for alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis cis-form olefin according to claim 1, special
Sign is that the catalyst selects Pd (OAc)2, dosage is the 10% of alkynes mole dosage；
The dosage of the NaOAc is 2 times of alkynes mole dosage, and the dosage of the TEOA is 2.5 times of alkynes mole dosage；
The alcohol is 95% ethyl alcohol, and dosage is 50 times of alkynes mole dosage；
The temperature of reduction reaction is 140 DEG C, and the reaction time is 30~40h.
3. the method for alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis cis-form olefin according to claim 1, special
Sign is, in the general structure of the alkynes, any one of R and R' in following each genes: alkyl, phenyl ring, naphthalene nucleus, pyrrole
Piperidinyl, alkylbenzene, alkoxy benzene, halogeno-benzene and silylation benzene.
4. a kind of method of alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis trans olefins, which is characterized in that including as follows
Step: by ligand R, R-DIPAMP, catalyst, alcohol and alkynes carry out the reduction reaction of alkynes in organic solvent, and reaction generates
Trans olefins；
Reduction reaction formula are as follows:
The general structure of the alkynes are as follows:
The reactor of reduction reaction is the voltage-resistant reactor of sealing, and the temperature of reduction reaction is 120~150 DEG C, reduction reaction
Time is 20~48h；
The dosage of the catalyst is the 5~20% of alkynes mole dosage；The dosage of the R, R-DIPAMP be alkynes mole with
0.5~5 times of amount, the dosage of the NaOAc are 0.5~5 times of alkynes mole dosage, and the dosage of the TEOA is alkynes mole
0.5~5 times of dosage, the dosage of the alcohol are 10~100 times of alkynes mole dosage；
Wherein, the organic solvent is acetonitrile；
The catalyst is selected from Pd (OAc)2、PdCl2, Pd/C and PdCl2(PPh3)2At least one of.
5. the method for alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis trans olefins according to claim 4, special
Sign is that the catalyst selects Pd (OAc)2, dosage is the 10% of alkynes mole dosage；
The dosage of the NaOAc is 2 times of alkynes mole dosage, and the dosage of the TEOA is 2.5 times of alkynes mole dosage；
The alcohol is 95% ethyl alcohol, and dosage is 50 times of alkynes mole dosage；
The temperature of reduction reaction is 145 DEG C, and the reaction time is 32~40h.
6. the method for alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis trans olefins according to claim 4, special
Sign is, in the general structure of the alkynes, any one of R and R' in following each groups: alkyl, phenyl ring, naphthalene nucleus, pyrrole
Piperidinyl, alkylbenzene, alkoxy benzene, halogeno-benzene and silylation benzene.
7. a kind of method that alcohol hydrogen supply palladium chtalyst reduction terminal alkyne is alkene, which comprises the steps of:
Under nitrogen gas protection, the reduction that TEOA, NaOAc, catalyst, alcohol and alkynes are carried out to alkynes in organic solvent is anti-
It answers, reaction generates the cis-form olefin；
Reaction equation are as follows:
The reactor of reduction reaction is the voltage-resistant reactor of sealing, and the temperature of reduction reaction is 60~100 DEG C, the reaction time 20
~30h；
The dosage of the catalyst is the 5~20% of alkynes mole dosage, and the dosage of the NaOAc is alkynes mole dosage
0.5~5 times, the dosage of the TEOA is 0.5~5 times of alkynes mole dosage, and the dosage of the alcohol is alkynes mole dosage
10~100 times；
The organic solvent is acetonitrile；
The catalyst is selected from Pd (OAc)2、PdCl2, Pd/C and PdCl2(PPh3)2At least one of.
8. the method that alcohol hydrogen supply palladium chtalyst reduction terminal alkyne according to claim 7 is alkene, which is characterized in that described
Catalyst selects Pd (OAc)2, dosage is the 10% of alkynes mole dosage；
The dosage of the NaOAc is 2 times of alkynes mole dosage, and the dosage of the TEOA is 2.5 times of alkynes mole dosage；
The alcohol is 95% ethyl alcohol, and dosage is 50 times of alkynes mole dosage；
The temperature of reduction reaction is 80 DEG C, and the reaction time is for 24 hours.
9. the method that alcohol hydrogen supply palladium chtalyst reduction terminal alkyne according to claim 7 is alkene, which is characterized in that described
In the general structure of alkynes, R and any one in following each groups: alkyl, phenyl ring, naphthalene nucleus, pyridyl group, alkylbenzene,
Alkoxy benzene, halogeno-benzene and silylation benzene.
10. the method that alcohol hydrogen supply palladium chtalyst reduction terminal alkyne according to claim 7 is alkene, which is characterized in that also
The environment of original reaction is under nitrogen protection.
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| 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 |
| CN112108175A (en) * | 2020-08-17 | 2020-12-22 | 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 |
| CN113443952A (en) * | 2021-07-15 | 2021-09-28 | 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 |
| CN113563150A (en) * | 2021-07-15 | 2021-10-29 | 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 |
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Cited By (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 |
| CN112108175A (en) * | 2020-08-17 | 2020-12-22 | 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 |
| CN113443952A (en) * | 2021-07-15 | 2021-09-28 | 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 |
| CN113563150A (en) * | 2021-07-15 | 2021-10-29 | 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 |
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