CN113443952A - Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing alkyne semi-reduction through iridium with hydrogen supplied by water - Google Patents
Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing alkyne semi-reduction through iridium with hydrogen supplied by water Download PDFInfo
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Abstract
The invention provides a method for selectively synthesizing cis-olefin and trans-olefin by catalyzing alkyne semi-reduction through iridium by water hydrogen supply, which comprises the following steps: carrying out alkyne reduction reaction on DPPE, COD, a catalyst, water and alkyne in an organic solvent, and reacting under the protection of nitrogen to generate cis-form alkene; ligand DPPE, a catalyst, water and alkyne are subjected to reduction reaction of alkyne in an organic solvent, and the reaction is carried out under the protection of nitrogen to generate trans-alkene; the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 100-130 ℃, 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, and the using amount of water is 10-50 times of the mol using amount of alkyne; the dosage of the ligand is 0.2-5 times of the molar dosage of the catalyst. 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 alkyne semi-reduction through iridium by water hydrogen supply.
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 having various biological activities (anti-tumor, anti-vascular-proliferation, cytotoxic and cytostatic, etc.) are isolated from natural products. For example, Combretastatin A-4 with cis-structure is a good antineoplastic drug, and is likely to become the first drug on the market in the anti-tubulin polymerization drugs. Resveratrol in trans-structure has very good antioxidant compounds. In addition, the compound is also a phenyl ethyl hydrazine Sulfate Salt which is synthesized by taking styrene with a terminal group as a raw material and has an antidepressant effect.
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 in Lindlar of Germany in 19523-PbO and Pd-BaS2O4Quinoline, two of which catalyze the selective reduction of alkynes to cis-alkenes by hydrogen, is widely used in synthetic chemistry, but suffers from 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 reduction reaction of alkyne into saturated alkane, so that the selectivity (chemical reaction selectivity) of the reduction reaction is not ideal, and the separation and purification of the product become difficult; (2) the reduction reaction uses conventional hydrogen as hydrogen source, and uses the reactionSpecial requirements are required in terms of response and safety; (3) trans olefins are not 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 Et3SiH is used as a hydrogen source to reduce diarylalkynes into cis-diarylenes in a two-step process with high selectivity2In the presence of a catalyst, an addition product of hydrosilane and diarylacetylene is first formed, and then the alkyl group is desilicated under reflux in the presence of equivalent 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 by iridium with hydrogen supplied by water, wherein the catalyst is cheap and easy to obtain, the reaction operation is simple, and the method is suitable for large-scale production; cheap water 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-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.
In order to solve the above technical problems, an embodiment of the present invention provides a method for selectively synthesizing cis-form olefin by iridium-catalyzed alkyne semi-reduction with water hydrogen supply, comprising the following steps:
carrying out alkyne reduction reaction on COD, DPPE, a catalyst, water and alkyne in an organic solvent to generate cis-form 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 100-130 ℃, 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 DPPE is 0.5-5 times of the mol using amount of the catalyst, the using amount of the COD is 0.5-5 times of the mol using amount of the alkyne, and the using amount of the water is 10-100 times of the mol using amount of the alkyne;
wherein the organic solvent is tetrahydrofuran, and the environment of the reduction reaction is under the protection of nitrogen.
Preferably, the catalyst is [ Ir (cod) Cl]2The using amount is 5 percent of the molar using amount of alkyne;
the dosage of the DPPE is 4 times of the molar dosage of the catalyst, and the dosage of the COD is 2.5 times of the molar dosage of the alkyne;
the water is a hydrogen source, and the dosage of the water is 50 times of the molar dosage of alkyne.
Preferably, the temperature of the reduction reaction is 120 ℃.
Wherein, in the alkyne structural general formula (II), R and R' are selected from any one of the following genes: alkyl, benzene, naphthalene, pyridyl, alkylbenzene, alkoxybenzene, halobenzene and silyl benzene.
The invention also provides a method for selectively synthesizing trans-olefin by catalyzing alkyne semi-reduction by iridium through water hydrogen supply, which comprises the following steps: carrying out reduction reaction of alkyne on ligand DPPE, a catalyst, water and alkyne in an organic solvent to generate trans-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 100-130 ℃, 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 DPPE is 0.5-5 times of the molar dosage of alkyne, the dosage of the COD is 0.5-5 times of the molar dosage of alkyne, and the dosage of the water is 10-100 times of the molar dosage of alkyne;
wherein the organic solvent is tetrahydrofuran.
Preferably, the catalyst is [ Ir (cod) Cl]2The using amount is 5 percent of the molar using amount of alkyne;
the dosage of the DPPE is 4 times of the molar dosage of the catalyst;
the hydrogen source is water, and the dosage is 50 times of the molar dosage of alkyne.
Preferably, the temperature of the reduction reaction is 120 ℃, and the environment of the reduction reaction is under the protection of nitrogen.
Wherein, in the general formula (IV), R and R' are selected from any one of the following groups: alkyl, benzene, naphthalene, pyridyl, alkylbenzene, alkoxybenzene, halobenzene and silyl benzene.
The invention also provides a method for catalytically reducing terminal alkyne into olefin by iridium through water hydrogen supply, which comprises the following steps:
carrying out alkyne reduction reaction on COD, DPPE, a catalyst, water and alkyne in an organic solvent to generate cis-form olefin;
the reaction formula is as follows:
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 60-100 ℃, and the reaction time is 20-30 h;
the amount of the catalyst is 5-20% of the molar amount of alkyne, the amount of the DPPE is 0.5-5 times of the molar amount of alkyne, and the amount of the water is 10-100 times of the molar amount of alkyne;
the organic solvent is tetrahydrofuran.
Preferably, the catalyst is [ Ir (cod) Cl]2The using amount is 5 percent of the molar using amount of alkyne;
the dosage of the DPPE is 4 times of the molar dosage of the catalyst;
the water is a hydrogen source, and the dosage of the water is 50 times of the molar dosage of alkyne.
Preferably, the temperature of the reduction reaction is 70 ℃, the reaction time is 24 hours, and the environment of the reduction reaction is under the protection of nitrogen.
Wherein, in the general structural formula (VI) of the alkyne, R is selected from any one of the following groups: alkyl, benzene, naphthalene, pyridyl, alkylbenzene, alkoxybenzene, halobenzene and silyl benzene.
The technical scheme of the invention has the following beneficial effects:
1. the invention uses water as hydrogen source, is cheap and easy to obtain, safe and efficient, economic and environment-friendly;
2. the method can efficiently and selectively obtain cis-olefin and trans-olefin, and 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. cheap water 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 catalytic system has strong universality to a substrate, and alkynes containing various functional groups can efficiently carry out high-selectivity reduction reaction.
Drawings
FIG. 1 is a hydrogen spectrum of a target product cis-stilbene 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 hydrogen spectrum of cis-2- (3-chlorophenyl) -1- (4-chlorophenyl) ethylene, which is a target product obtained in example 2 of the present invention;
FIG. 4 is a carbon spectrum of cis-2- (3-chlorophenyl) -1- (4-chlorophenyl) ethylene, a target product obtained in example 2 of the present invention;
FIG. 5 is a hydrogen spectrum of trans-stilbene which is a target product obtained in example 3 of the present invention;
FIG. 6 is a carbon spectrum diagram of trans-stilbene which is a target product obtained in example 3 of the present invention;
FIG. 7 is a hydrogen spectrum of trans-1- (4-chlorostyryl) -4-methylbenzene, which is a target product obtained in example 4 of the present invention;
FIG. 8 is a carbon spectrum diagram of trans-1- (4-chlorostyryl) -4-methylbenzene, a target product obtained in example 4 of the present invention;
FIG. 9 is a chart showing the hydrogen spectrum of styrene, the target product obtained in example 5 of the present invention;
FIG. 10 is a carbon spectrum of styrene, a target product obtained in example 5 of the present invention;
FIG. 11 is a hydrogen spectrum of 4-chlorostyrene, the target product obtained in example 6 of the present invention;
FIG. 12 is a carbon spectrum of 4-chlorostyrene, the target product obtained in example 6 of the present invention.
Detailed Description
In order 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 iridium by water hydrogen supply, which comprises the following steps:
carrying out alkyne reduction reaction on COD, DPPE, a catalyst, water and alkyne in an organic solvent to generate cis-form 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 amount of the catalyst is 5-20% of the molar amount of alkyne, the amount of the DPPE is 0.5-5 times of the molar amount of alkyne, the amount of the COD is 0.5-5 times of the molar amount of alkyne, and the amount of the water is 10-100 times of the molar amount of alkyne;
wherein the organic solvent is tetrahydrofuran, and the environment of the reduction reaction is under the protection of nitrogen.
The catalyst is [ Ir (cod) Cl]2The using amount is 5 percent of the molar using amount of alkyne;
the dosage of the DPPE is 4 times of the molar dosage of the catalyst, and the dosage of the COD is 2.5 times of the molar dosage of the alkyne; the hydrogen source is water, and the using amount of the water is 50 times of the molar using amount of alkyne; the temperature of the reduction reaction is 140 ℃, and the reaction time is 24-30 h.
Wherein, in the alkyne structural general formula (II), R and R' are selected from any one of the following genes: alkyl, benzene, naphthalene, pyridyl, alkylbenzene, alkoxybenzene, halobenzene and silyl benzene.
The following describes a method for selectively synthesizing cis-olefins by using iridium under the catalysis of water hydrogen supply to alkyne semi-reduction.
Example 1
N2Under protection, diphenylacetylene (0.20mmol) and [ Ir (cod) Cl were added into a 15ml pressure-resistant tube]2(0.01mmol,6.71mg)、DPPE(0.04mmol，15.9mg)、COD(0.4mmol,49μL)、H2O (10mmol, 180. mu.L) and THF (1.5mL) were stirred at 120 ℃ 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
N2Under protection, 2- (3-chlorophenyl) -1- (4-chlorophenyl) acetylene (0.20mmol) and [ Ir (cod) Cl were added into a 15ml pressure-resistant tube]2(0.01mmol,6.71mg)、DPPE(0.04mmol，15.9mg)、COD(0.4mmol,49μL)、H2O (10mmol, 180. mu.L) and THF (1.5mL) were stirred at 120 ℃ 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 45.32mg in 91% yield.
FIG. 3 shows a hydrogen spectrum of cis-2- (3-chlorophenyl) -1- (4-chlorophenyl) ethylene, which is the objective product obtained in example 4, and FIG. 4 shows a carbon spectrum of cis-2- (3-chlorophenyl) -1- (4-chlorophenyl) ethylene, which is the objective product obtained in example 4, and it can be seen from FIGS. 3 and 4 that the structure of this product is correct.
The invention also provides a method for selectively synthesizing trans-olefin by catalyzing alkyne semi-reduction by iridium through water hydrogen supply, which comprises the following steps: carrying out reduction reaction of alkyne on ligand DPPE, a catalyst, water and alkyne in an organic solvent to generate trans-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 dosage of the DPPE is 0.5-5 times of the molar dosage of the catalyst, and the dosage of the water is 10-100 times of the molar dosage of alkyne;
wherein the organic solvent is tetrahydrofuran, and the environment of the reduction reaction is under the protection of nitrogen.
Preferably, the catalyst is [ Ir (cod) Cl]2The amount is 5% of the molar amount of alkyne.
The dosage of the DPPE is 4 times of the molar dosage of the catalyst; the water is a hydrogen source, and the using amount of the water is 50 times of the molar using amount of alkyne; the temperature of the reduction reaction is 70 ℃, and the reaction time is 32-40 h.
Wherein, in the general formula (IV) 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 method for selectively synthesizing the trans-olefin by catalyzing alkyne semi-reduction through iridium by water hydrogen supply is further illustrated by combining specific examples.
Example 3
N2Under protection, diphenylacetylene (0.20mmol) and [ Ir (cod) Cl were added into a 15ml pressure-resistant tube]2(0.01mmol,6.71mg)、DPPE(0.04mmol，15.9mg)、H2O (10mmol, 180. mu.L) and THF (1.5mL) were stirred at 120 ℃ 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, and the white solid is 34.2mg, and the yield is 95%.
Fig. 5 shows a hydrogen spectrum of the target product trans-stilbene obtained in example 3, and fig. 6 shows a carbon spectrum of the target product trans-stilbene obtained in example 3, and it can be seen from fig. 5 and 6 that the structure of the product is correct.
Example 4
N2Under protection, 1- (4-chlorophenylethynyl) -4-methylbenzene (0.20mmol) and [ Ir (cod) Cl are added into a 15ml pressure resistant tube]2(0.01mmol,6.71mg)、DPPE(0.04mmol，15.9mg)、H2O (10mmol, 180. mu.L) and THF (1.5mL) were stirred at 120 ℃ 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 was purified by column chromatography to give trans-1- (4-chlorostyryl) -4-methylbenzene as a white solid (34.2 mg, 75% yield).
Fig. 7 is a hydrogen spectrum and fig. 8 is a carbon spectrum of the target product, trans-stilbene, of example 4, and it can be seen from fig. 7 and 8 that the structure of the target product is correct.
The invention also provides a method for catalytically reducing terminal alkyne into olefin by iridium through water hydrogen supply, which comprises the following steps:
under the protection of inert gas, carrying out reduction reaction on DPPE, a catalyst, water and alkyne in an organic solvent to generate the terminal group olefin;
the reaction formula is as follows:
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 60-100 ℃, and the reaction time is 20-30 h;
the amount of the catalyst is 5-20% of the molar amount of alkyne, the amount of the DPPE is 0.5-5 times of the molar amount of alkyne, the amount of the COD is 0.5-5 times of the molar amount of alkyne, and the amount of the water is 10-100 times of the molar amount of alkyne;
the organic solvent is tetrahydrofuran, and the environment of the reduction reaction is under the protection of nitrogen.
Preferably, the catalyst is [ Ir (cod) Cl]2The using amount is 5 percent of the molar using amount of alkyne;
the dosage of the DPPE is 2 times of the molar dosage of the catalyst; the water is a hydrogen source, and the using amount of the water is 50 times of the molar using amount of alkyne; the temperature of the reduction reaction is 70 ℃, and the reaction time is 24 h.
Wherein, in the general structural formula (VI) of the alkyne, R is selected from any one of the following groups: alkyl, benzene, naphthalene, pyridyl, alkylbenzene, alkoxybenzene, halobenzene and silyl benzene.
The method of iridium-catalyzed reduction of terminal alkynes to alkenes using water to provide hydrogen is further described below with reference to specific examples.
Example 5
N2Under protection, the mixture is added into a 15ml pressure-resistant pipePhenylacetylene (0.20mmol), [ Ir (cod) Cl]2(0.01mmol,6.71mg)、DPPE(0.04mmol，15.9mg)、H2O (10mmol, 180. mu.L) and THF (1.5mL) were stirred at 70 ℃ 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, and the colorless liquid is 12.64mg, and the yield is 61%.
Fig. 9 shows a hydrogen spectrum of styrene, which is the target product obtained in example 5, and fig. 10 shows a carbon spectrum of styrene, which is the target product obtained in example 5, and it can be seen from fig. 9 and 10 that the structure of the product is correct.
Example 6
N2Under protection, 4-chlorophenylacetylene (0.20mmol) and [ Ir (cod) Cl were added into a 15ml pressure-resistant tube]2(0.01mmol,6.71mg)、DPPE(0.04mmol，15.9mg)、H2O (10mmol, 180. mu.L) and THF (1.5mL) were stirred at 70 ℃ 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 was purified by column chromatography to give 4-chlorostyrene in 20.72mg as a colorless liquid in 75% yield.
Fig. 11 shows a hydrogen spectrum of the target product 4-vinylbiphenyl obtained in example 6, and fig. 12 shows a carbon spectrum of the target product 4-vinylbiphenyl obtained in example 6, and it can be seen from fig. 11 and 12 that the structure of the product is correct.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for selectively synthesizing cis-olefin by catalyzing alkyne semi-reduction through iridium with hydrogen supplied by water is characterized by comprising the following steps:
carrying out alkyne reduction reaction on COD, DPPE, a catalyst, water and alkyne in an organic solvent to generate cis-form 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 100-130 ℃, 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 DPPE is 0.5-5 times of the mol using amount of the catalyst, the using amount of the COD is 0.5-5 times of the mol using amount of the alkyne, and the using amount of the water is 10-100 times of the mol using amount of the alkyne;
wherein the organic solvent is tetrahydrofuran, and the environment of the reduction reaction is under the protection of nitrogen.
2. The method for selectively synthesizing cis-form olefin by using iridium under water hydrogen supply catalysis and semi-reduction of alkyne, according to claim 1, wherein the catalyst is [ Ir (cod) Cl]2The using amount is 5 percent of the molar using amount of alkyne;
the dosage of the DPPE is 2 times of the molar dosage of the catalyst, and the dosage of the COD is 2 times of the molar dosage of the alkyne;
the hydrogen source is water, and the using amount of the water is 50 times of the molar using amount of alkyne;
the temperature of the reduction reaction was 120 ℃.
3. The method for selectively synthesizing cis-form olefin by catalyzing alkyne with iridium by water-hydrogen supply according to claim 1, wherein in the general structural formula (II) of alkyne, R and R' are selected from any one of the following genes: alkyl, benzene, naphthalene, pyridyl, alkylbenzene, alkoxybenzene, halobenzene and silyl benzene.
4. A method for selectively synthesizing trans-olefin by catalyzing alkyne semi-reduction through iridium with hydrogen supplied by water is characterized by comprising the following steps: carrying out reduction reaction of alkyne on ligand DPPE, a catalyst, water and alkyne in an organic solvent to generate trans-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 100-130 ℃, 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 t-Bu2The using amount of the PCl is 0.5-5 times of the mol using amount of alkyne, the using amount of the DPPE is 0.5-5 times of the mol using amount of the catalyst, the using amount of the COD is 0.5-5 times of the mol using amount of the alkyne, and the using amount of the water is 10-100 times of the mol using amount of the alkyne;
wherein the organic solvent is tetrahydrofuran.
5. The method for selectively synthesizing trans-olefin through semi-reduction of alkyne catalyzed by iridium on hydrogen supply with water according to claim 4, wherein the catalyst is [ Ir (cod) Cl]2The using amount is 5 percent of the molar using amount of alkyne;
the dosage of the DPPE is 2 times of the molar dosage of the catalyst, and the dosage of the COD is 2.5 times of the molar dosage of the alkyne;
the hydrogen source is water, and the using amount of the water is 50 times of the molar using amount of alkyne;
the temperature of the reduction reaction is 120 ℃, and the environment of the reduction reaction is under the protection of nitrogen.
6. The method for selectively synthesizing the trans-olefin by the semi-reduction of the alkyne catalyzed by the iridium hydride with water as the hydrogen donor according to claim 4, wherein in the general structural formula (IV) 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.
7. A method for catalytically reducing end group alkyne into olefin by iridium through hydrogen supply by water is characterized by comprising the following steps:
under the protection of nitrogen gas, carrying out alkyne reduction reaction on COD, DPPE, a catalyst, water and alkyne in an organic solvent to generate cis-form olefin;
the reaction formula is as follows:
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 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 DPPE is 0.5-5 times of the mol using amount of the catalyst, the using amount of the COD is 0.5-5 times of the mol using amount of the alkyne, and the using amount of the water is 10-100 times of the mol using amount of the alkyne;
the organic solvent is tetrahydrofuran.
8. The method of claim 7The method for catalytically reducing terminal alkyne into olefin by iridium with hydrogen supplied by water is characterized in that [ Ir (cod) Cl ] is selected as the catalyst]2The using amount is 5 percent of the molar using amount of alkyne;
the dosage of the DPPE is 2 times of the molar dosage of the catalyst, and the dosage of the COD is 2.5 times of the molar dosage of the alkyne;
the hydrogen source is water, and the using amount of the water is 50 times of the molar using amount of alkyne;
the temperature of the reduction reaction is 70 ℃, and the reaction time is 24 h.
9. The method of iridium catalytic reduction of terminal alkynes to alkenes as claimed in claim 7 wherein the alkynes have the general structural formula (VI) wherein R is selected from any one of the following groups: alkyl, benzene, naphthalene, pyridyl, alkylbenzene, alkoxybenzene, halobenzene and silyl benzene.
10. The method of iridium-catalysed reduction of terminal alkynes to alkenes according to claim 7, wherein the environment of the reduction reaction is under nitrogen.
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| CN109134172A (en) * | 2018-09-12 | 2019-01-04 | 南通大学 | The alcohol hydrogen supply iridium catalytic selectivity of ligand regulation synthesizes Z- and E- olefins process |
| CN109776253A (en) * | 2018-12-27 | 2019-05-21 | 南通大学 | Alcohol hydrogen supply palladium chtalyst alkynes semi-reduction selectivity synthesis is suitable, trans olefins methods |
| CN109942364A (en) * | 2019-04-12 | 2019-06-28 | 云南民族大学 | It is a kind of using water as the olefin synthesis process of hydrogen source |
| CN113024340A (en) * | 2021-03-18 | 2021-06-25 | 长春工业大学 | Method for reducing alkyne into olefin by using water as hydrogen source under catalysis of nickel |
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| CN109134172A (en) * | 2018-09-12 | 2019-01-04 | 南通大学 | The alcohol hydrogen supply iridium catalytic selectivity of ligand regulation synthesizes Z- and E- olefins process |
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