CN113443952B - 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 olefin; carrying out alkyne reduction reaction on ligand DPPE, a catalyst, water and alkyne in an organic solvent, and reacting under the protection of nitrogen to generate trans-olefin; 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 dosage of the catalyst is 5 to 20 percent of the molar dosage of alkyne, and the dosage of water is 10 to 50 times of the molar dosage of alkyne; the dosage of the ligand is 0.2 to 5 times of the molar dosage of the catalyst. The catalyst system has extremely high chemical reaction and stereoselectivity, and can synthesize cis-or trans-olefin products with high yield; the catalyst system has strong universality for substrates, 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 with hydrogen supplied by water.
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 having various biological activities (anti-tumor, anti-vascular proliferation, cytotoxic and cytostatic properties, etc.) containing 1, 2-stilbene structural units 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 used in Lindlar of Germany in 1952 3 -PbO and Pd-BaS 2 O 4 Quinoline, 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 traditional hydrogen as a hydrogen source, and special requirements are needed in the aspects of reactor use 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, (Menan Tokmic) was synthesized by (MesCCC) Co (N) 2 )(PPh 3 ) 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 (e.g. 1,3 diyne, alkyne esters etc.) is not ideal, trans olefins are difficult to obtain, while formic acid is expensive, especially the ligand NHC is very expensive, limiting its large scale use. Alami Et al reported silane Et 3 SiH is used as a hydrogen source to reduce diarylalkynes into cis-diarylenes in a two-step process with high selectivity 2 CatalysisIn the presence of an agent, 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 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-or trans-olefin products with high yield; the catalyst system has strong universality for substrates, 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 dosage of the catalyst is 5-20% of the molar dosage of alkyne, the dosage of the DPPE is 0.5-5 times of the molar dosage of the catalyst, 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, and the environment of the reduction reaction is under the protection of nitrogen.
Preferably, the catalyst is [ Ir (cod) Cl] 2 The 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;
and the water is used as a hydrogen source, and the using amount of the water is 50 times of the molar using amount 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 silylbenzene.
The invention also provides a method for selectively synthesizing trans-olefin by catalyzing alkyne semi-reduction by iridium with hydrogen supplied by water, which comprises the following steps: carrying out alkyne reduction reaction on ligand DPPE, a catalyst, water and alkyne 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 100-130 ℃, and the time of the reduction reaction is 20-48 h;
the dosage of the catalyst is 5 to 20 percent of the molar dosage 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] 2 The 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 the terminal alkyne into the olefin by iridium with hydrogen supplied by water, 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 dosage of the catalyst is 5-20% of the molar dosage of alkyne, the dosage of the DPPE 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;
the organic solvent is tetrahydrofuran.
Preferably, the catalyst is [ Ir (cod) Cl] 2 The 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 silylbenzene.
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 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 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 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 chart showing the carbon spectrum of styrene, the 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 according to 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 with 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 dosage of the catalyst is 5-20% of the molar dosage 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, and the environment of the reduction reaction is under the protection of nitrogen.
The catalyst is [ Ir (cod) Cl] 2 The 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 structural general formula (II) of the alkyne, 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
N 2 Under protection, tolane (0.20 mmol) 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)、H 2 O (10 mmol, 180. Mu.L) and THF (1.5 mL) 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 Na 2 SO 4 Drying, and concentrating under reduced pressure. The crude product is separated and purified by column chromatography to obtain cis-bisStyrene, 32.4mg as a colorless liquid, in 90% yield.
Fig. 1 shows a hydrogen spectrum of the target product cis-stilbene obtained in example 1, and fig. 2 shows respective carbon spectra 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
N 2 Under protection, 2- (3-chlorophenyl) -1- (4-chlorophenyl) acetylene (0.20 mmol) 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)、H 2 O (10mmol, 180. Mu.L) and THF (1.5 mL) 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 Na 2 SO 4 Drying, 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 dosage of the catalyst is 5 to 20 percent of the molar dosage of alkyne; the dosage of the DPPE is 0.5 to 5 times of the molar dosage of the catalyst, and the dosage of the water is 10 to 100 times of the molar dosage 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] 2 The 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), R and R' are selected from any one of the following groups: alkyl, benzene, naphthalene, pyridyl, alkylbenzene, alkoxybenzene, halobenzene and silylbenzene.
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
N 2 Under protection, tolane (0.20 mmol) and [ Ir (cod) Cl were added into a 15ml pressure resistant tube] 2 (0.01mmol,6.71mg)、DPPE(0.04mmol，15.9mg)、H 2 O (10 mmol, 180. Mu.L) and THF (1.5 mL) 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 Na 2 SO 4 Drying, 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
N 2 Under protection, 1- (4-chlorophenylethynyl) -4-methylbenzene (0.20 mmol) and [ Ir (cod) Cl are added into a 15ml pressure resistant tube] 2 (0.01mmol,6.71mg)、DPPE(0.04mmol，15.9mg)、H 2 O (10 mmol, 180. Mu.L) and THF (1.5 mL) 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 Na 2 SO 4 Drying, 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 of trans-stilbene obtained in example 4, and it can be seen from fig. 7 and 8 that the structure of the target product of trans-stilbene 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 of alkyne 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 dosage of the catalyst is 5-20% of the molar dosage 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;
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] 2 The 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 24h.
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 following examples are provided to further illustrate the iridium-catalyzed reduction of terminal alkynes to alkenes with water-hydrogen donating.
Example 5
N 2 Under protection, phenylacetylene (0.20 mmol) and [ Ir (cod) Cl are added into a 15ml pressure resistant tube] 2 (0.01mmol,6.71mg)、DPPE(0.04mmol，15.9mg)、H 2 O (10 mmol, 180. Mu.L) and THF (1.5 mL) 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 Na 2 SO 4 Drying, 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
N 2 Under protection, 4-chlorophenylacetylene (0.20 mmol) and [ Ir (cod) Cl were added into a 15ml pressure-resistant tube] 2 (0.01mmol,6.71mg)、DPPE(0.04mmol，15.9mg)、H 2 O (10mmol, 180. Mu.L) and THF (1.5 mL) were stirred at 70 ℃ for 24 hours.
After the reaction is finished, cooling to room temperature, and adding acetic acid10mL of ethyl ester, washing the organic phase with saturated brine 3 times, and adding anhydrous Na to the organic phase 2 SO 4 Drying, 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 (6)
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:
mixing COD, DPPE and catalyst [ Ir (COD) Cl ]] 2 Carrying out reduction reaction of alkyne in an organic solvent by water and alkyne to generate cis-form alkene;
reduction reaction formula (1)
) Comprises the following steps:
the structural general formula of alkyne (I)
) Comprises the following steps:
the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 100 to 130 ℃, and the time of the reduction reaction is 20 to 48h;
the catalyst [ Ir (cod) Cl] 2 The dosage of the catalyst is 5-20% of the molar dosage of alkyne, the dosage of the DPPE is 0.5-5 times of the molar dosage of the catalyst, 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, and the environment of the reduction reaction is under the protection of nitrogen;
the structural general formula of alkyne (I)
) Wherein R and R' are selected from any one of the following genes: alkyl, phenyl, naphthyl, pyridyl, alkylphenyl, alkoxyphenyl, halophenyl and silylphenyl.
2. The method for selectively synthesizing cis-form olefin by catalyzing alkyne through iridium with hydrogen supplied by water in semi-reduction mode according to claim 1, wherein [ Ir (cod) Cl ] is selected as the catalyst] 2 The 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 dosage of the water is 50 times of the molar dosage of the alkyne;
the temperature of the reduction reaction was 120 ℃.
3. 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: ligand DPPE, catalyst [ Ir (cod) Cl] 2 Carrying out reduction reaction of alkyne on water and alkyne in an organic solvent to generate trans-alkene;
reduction reaction formula (A)
) Comprises the following steps:
the alkyne has a general structural formula (
) Comprises the following steps:
the reactor of the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 100 to 130 ℃, and the time of the reduction reaction is 20 to 48h;
the catalyst [ Ir (cod) Cl ]] 2 The dosage of the catalyst is 5 to 20 percent of the molar dosage of alkyne; the dosage of the DPPE is 0.5 to 5 times of the molar dosage of the catalyst, and the dosage of the water is 10 to 100 times of the molar dosage of alkyne;
wherein the organic solvent is tetrahydrofuran;
the structural general formula of alkyne (I)
) Wherein R and R' are selected from any one of the following groups: alkyl, phenyl, naphthyl, pyridyl, alkylphenyl, alkoxyphenyl, halophenyl and silylphenyl.
4. The method for selectively synthesizing trans-olefin through semi-reduction of alkyne catalyzed by iridium on hydrogen supply by water according to claim 3, wherein the catalyst is [ Ir (cod) Cl] 2 The 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 dosage of the water is 50 times of the molar dosage of the alkyne;
the temperature of the reduction reaction is 120 ℃, and the environment of the reduction reaction is under the protection of nitrogen.
5. 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, DPPE and catalyst [ Ir (cod) Cl] 2 Carrying out reduction reaction of water and alkyne in an organic solvent to generate the cis-form alkene;
reaction formula (I)
) Comprises the following steps:
the structural general formula of alkyne (I)
) Comprises the following steps:
the reactor for the reduction reaction is a sealed pressure-resistant reactor, the temperature of the reduction reaction is 60 to 100 ℃, and the reaction time is 20 to 30h;
the catalyst [ Ir (cod) Cl] 2 The dosage of the compound is 5-20% of the molar dosage 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 the alkyne;
the organic solvent is tetrahydrofuran;
the structural general formula of alkyne (I)
) Wherein R is selected from any one of the following groups: alkyl, phenyl, naphthyl, pyridyl, alkylphenyl, alkoxyphenyl, halophenyl and silylphenyl.
6. The iridium-catalysed hydrogen-donating reduction-end-group alkyne of claim 5 as an alkeneThe method is characterized in that the catalyst adopts [ Ir (cod) Cl] 2 The 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 dosage of the water is 50 times of the molar dosage of the alkyne;
the temperature of the reduction reaction is 70 ℃, and the reaction time is 24h.
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