CN105218335A - A kind of method being prepared chirality geranial by citral asymmetric catalytic hydrogenation - Google Patents

A kind of method being prepared chirality geranial by citral asymmetric catalytic hydrogenation Download PDF

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CN105218335A
CN105218335A CN201510685884.3A CN201510685884A CN105218335A CN 105218335 A CN105218335 A CN 105218335A CN 201510685884 A CN201510685884 A CN 201510685884A CN 105218335 A CN105218335 A CN 105218335A
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iodide
chirality
citral
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ammonium
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CN105218335B (en
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张万斌
张振锋
陈建中
董菁
鲍元野
张永振
黎源
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Wanhua Chemical Group Nutrition Technology Co ltd
Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds

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Abstract

The present invention relates to a kind of method being prepared chirality geranial by citral asymmetric catalytic hydrogenation of chemical technology field.Under additive (as sodium iodide, four n-octyl brometo de amonios, benzyltriethylammonium chloride etc.) effect, by chirality Rhodium Complexes Catalyzed, E formula and/or Z formula citral is made to be R or S chirality geranial by asymmetric mode hydrogenation.Further, can by changing the chirality of chiral catalyst, catalysis E formula or Z formula citral respectively, and obtain the chirality geranial of required same configuration.Thus reach the chirality geranial all configuration citrals being converted into completely required a kind of configuration.Reaction method mild condition of the present invention, easy and simple to handle, and good reaction yield and reaction efficiency can be realized, there is good effect.

Description

A kind of method being prepared chirality geranial by citral asymmetric catalytic hydrogenation
Technical field
That the present invention relates to is a kind of preparation method of chemical technology field chirality geranial, and specifically a kind of synthetic method by citral asymmetric rhodium catalysis hydrogenation synthesis of chiral geranial, belongs to essence and flavoring agent field.
Background technology
Geranial is a kind of important fragrance component, is also the precursor of many essence and flavoring agents, as can be used to other spices such as synthesis of hydroxy geranial and menthol.Particularly synthesize most important intermediate in menthol.Also be widely used in perfuming and the preparation of beverage, candy, food etc. simultaneously.Therefore, for geranial, particularly the demand of chirality geranial constantly increases.Thus, therefore its synthetic method is also subject to the attention of scientific research personnel and each company always.The patent of current synthesis of chiral geranial has a several section, and its synthetic method is mainly divided into enzyme catalysis, small molecules catalysis, dual catalyst catalysis, metal catalytic etc.Wherein, enzyme catalysis and small molecules catalysis process, efficiency and output are all very limited, are unfavorable for large-scale commercial production; Dual catalyst catalyst operation is complicated, and yield and enantioselectivity all need further raising.
By having very large researching value and economic worth to citral metal catalyzed hydrogenation synthesis of chiral geranial, it mainly contains following several synthetic method:
EP0000315 describes a kind of by under the existence of the catalyst complexes that be made up of rhodium and chiral phosphine, hydrogenation geranic acid or neral and prepare the method for optical activity geranial.
J.Mol.Cat.1982,16,51-59 and Helv.Chim.Acta2001,84, in 230-242, author have employed the title complex hydrogenation a of rhodium carbonyl and chiral diphosphine ligand respectively, beta-unsaturated aldehyde, and be applied to hydrogenation geranic acid or optically active geranial prepared by neral, transformation efficiency, enantioselectivity all have much room for improvement.
China's report such as publication CN101039894A, CN101675020A and CN101932543A uses the title complex homogeneous catalytic hydrogenation neral of rhodium carbonyl and chiral phosphine to prepare optically active geranial, and catalyzer is first through CO and H 2gas mixture is prefabricated, reacts at the H being mixed with a small amount of CO 2in carry out.
These metal catalyzed process above-mentioned mostly need the effect by poisonous CO gas, control the selectivity of reacting, or need the title complex of previously prepared rhodium carbonyl and chiral phosphine as catalyzer, technique is comparatively loaded down with trivial details, less stable, catalyst levels is higher, and cost is higher, carries out industrial applications so more difficult.
The present invention, by adding the method for additive simply, under the hydrogen of safely cleaning and the condition of gentleness, uses chirality rhodium complex simple and easy to get as catalyzer, geranic acid or neral is converted into geranial.The method has that technique is simple, enantioselectivity and the outstanding advantages such as productive rate is high and catalyst levels is low, has obvious industrial applications advantage.
Summary of the invention
The object of this invention is to provide a kind of method being prepared chirality geranial by citral asymmetric catalytic hydrogenation.This preparation method carries out shortening by adopting chirality rhodium complex, adds additive simultaneously, improves, control its stereoselectivity further, achieve asymmetric catalytic hydrogenation and prepare chirality geranial efficiently chemo-selective synthesis geranial.
In order to realize above goal of the invention, the present invention is achieved by the following technical solutions:
A kind of method being prepared chirality geranial by citral asymmetric catalytic hydrogenation: under the effect of chirality rhodium complex catalyst and additive, asymmetric hydrogenation is carried out to citral, preparation R or S chirality geranial.
The reaction method of asymmetric rhodium catalysis using hydrogenating citral of the present invention, reaction process can represent with following reaction formula:
In above-mentioned reaction formula, (1) represents citral, and (2) represent chirality geranial.Wherein, Additive represents additive, and Solvent represents solvent.
In the present invention, described chirality rhodium complex is formed by the rhodium salt and chiral ligand coordination with negatively charged ion and assistant ligand; The use-pattern of described catalyzer be described in there is the rhodium salt of negatively charged ion and assistant ligand and the coordination of chiral ligand direct in-situ after use, or directly use described chirality rhodium complex; The use-pattern of preferred catalyzer be described in there is the rhodium salt of negatively charged ion and assistant ligand and the coordination of chiral ligand direct in-situ after use, during complexed in situ, the mol ratio of rhodium and chiral ligand L* is 1:1 ~ 1.2, is preferably 1:1 ~ 1.1.
In the present invention, the structural formula of described chirality rhodium complex is [Rh (L*) (L)] X, and the rhodium salt structural formula with negatively charged ion and assistant ligand is [Rh (L) 2] X or [RhX (L)] 2, wherein, L* is chiral ligand, and L is assistant ligand, and X is negatively charged ion.
In the present invention, described asymmetric hydrogenation can carry out under the condition having solvent, also can carry out under condition of no solvent, carry out described asymmetric hydrogenation under an atmosphere of hydrogen; E formula and/or Z formula citral are first dissolved in solvent when having and carrying out under solvent condition by described asymmetric hydrogenation.
In the present invention, the purity of described citral is 99.0 ~ 99.9wt%, and in described citral, the ratio of E and Z configuration is 1:99 ~ 99:1.
Solvent of the present invention is the one or two or more in non-alkane polar solvent, non-polar solvent or protic solvent; Wherein, described non-alkane polar solvent is preferably methylene dichloride, 1,2-ethylene dichloride, DMF, acetone or acetonitrile; Non-polar solvent is preferably toluene, ether or tetrahydrofuran (THF); Described protic solvent is preferably methyl alcohol, ethanol, Virahol or trifluoroethanol; Solvent of the present invention is more preferably the one or two or more in toluene, methylene dichloride, 1,2-ethylene dichloride, ether, tetrahydrofuran (THF), methyl alcohol, ethanol, Virahol and trifluoroethanol.
In the present invention, the mass concentration of described citral is 0.5 ~ 100wt%, is preferably 30 ~ 100wt%, based on the total mass of citral and described solvent.
In the present invention, the negatively charged ion X in described chirality rhodium complex is Cl -, BF 4 -, SbF 6 -, CF 3cOO -or PF 6 -, be preferably BF 4 -, SbF 6 -or PF 6 -, more preferably BF 4 -or SbF 6 -.
In the present invention, the assistant ligand L in described chirality rhodium complex is diene ligand, is preferably pungent two rare (COD) of 1,5-ring or 2,5-norbornadiene (NBD).
In the present invention, the chiral ligand L* in described chirality rhodium complex is chiral diphosphine or phosphine nitrogen ligand, and described chiral ligand is selected from any one part in L1 ~ L17, and wherein, the configuration of ligand L 1 ~ L6 can be that the structural formula of R or S, L1 ~ L17 is as follows:
As preferred scheme, chiral ligand described in the present invention is L1 ~ L4, L7 ~ L11, L12 or L15, is more preferably L1, L3, L8, L11, L14 or L15, more preferably L1, L8 or L11, and Ar represents a:C respectively 6h 5, b:4-CH 3oC 6h 4, c:4-CF 3c 6h 4or d:3,5-di-tBu-4-MeOC 6h 2.
In the present invention, the mol ratio of described chirality rhodium complex and citral is 1:100 ~ 100000, is preferably 1:1000 ~ 50000, is more preferably 1:10000 ~ 50000.
In the present invention, carry out under effect while catalyzer and additive during described asymmetric hydrogenation, complexing is there is in the lone-pair electron on additive molecule and the unoccupied orbital in catalyst molecule with the form effect of δ key, catalyzer is being changed with substrate Coordinate property, catalyzer carbon-carbon double bond that is preferential and substrate is made to carry out coordination, and not with C=O bond coordination, thus carry out asymmetric hydrogenation on carbon-carbon double bond.
In the present invention, described additive is the one or two or more in iodide, bromide and muriate, and described iodide are sodium iodide, potassiumiodide, ammonium iodide, calcium iodide, zinc iodide, lithium iodide, tetrabutylammonium iodide, phenyl triethylammonium ammonium iodide, (ferrocenyl methyl) trimethylammonium ammonium iodide, ethyl three n-propyl ammonium iodide, four n-octyl ammonium iodides, (propyl group carbonic acyl radical sulphur ethyl) trimethylammonium ammonium iodide, 4-hexyl iodide, four n-heptyl ammonium iodides and 3-(trifluoromethyl) phenyl trimethicone ammonium iodide; Described bromide is brometo de amonio, phenyl triethylammonium brometo de amonio, (ferrocenyl methyl) trimethylammonium bromide, ethyl three n-propyl brometo de amonio, four n-octyl brometo de amonios, (propyl group carbonic acyl radical sulphur ethyl) trimethylammonium bromide, four hexyl brometo de amonios, four n-heptyl brometo de amonios and 3-(trifluoromethyl) phenyltrimethylammonium bromide; Described muriate is ammonium chloride, benzyltriethylammonium chloride, (ferrocenyl methyl) trimethyl ammonium chloride, ethyl three n-propyl ammonium chloride, four n-octyl ammonium chlorides, (propyl group carbonic acyl radical sulphur ethyl) trimethyl ammonium chloride, four hexyl ammonium chlorides, four n-heptyl ammonium chlorides or 3-(trifluoromethyl) phenyl trimethicone ammonium chloride; Described additive is preferably the one or two or more in sodium iodide, potassiumiodide, tetrabutylammonium iodide, phenyl triethylammonium ammonium iodide, (ferrocenyl methyl) trimethylammonium ammonium iodide, 4-hexyl iodide, four n-octyl brometo de amonios, four hexyl brometo de amonios, benzyltriethylammonium chloride and four hexyl ammonium chlorides; Be more preferably the one or two or more in sodium iodide, potassiumiodide, tetrabutylammonium iodide, four n-octyl brometo de amonios, four hexyl brometo de amonios, four hexyl ammonium chlorides and benzyltriethylammonium chloride; One or two or more more preferably in sodium iodide, tetrabutylammonium iodide, four n-octyl brometo de amonios and benzyltriethylammonium chloride.
In the present invention, the mol ratio of described additive and substrate citric aldehyde is 1:1 ~ 20, is preferably 1:5 ~ 10.
In the present invention, the nitrogen atmosphere pressure (gauge pressure) of described asymmetric hydrogenation is 1 ~ 80bar, is preferably 10 ~ 45bar, is more preferably 20 ~ 35bar.The bulk purity of hydrogen is 99.9 ~ 99.999v%.
In the present invention, the temperature of reaction of described asymmetric hydrogenation is-80 DEG C ~ 80 DEG C, is preferably 0 DEG C ~ 60 DEG C, is more preferably 15 DEG C ~ 35 DEG C; Reaction times is 1 ~ 72 hour, is preferably 5 ~ 36 hours, is more preferably 10 ~ 24 hours.
In the present invention, the optical purity of chirality geranial prepared by asymmetric hydrogenation citral can reach 72% ~ 98%, and product yield can reach 71% ~ 99%.
Beneficial effect of the present invention is:
1, carry out under effect while catalyzer and additive during asymmetric hydrogenation of the present invention, additive and catalyst complex, catalyzer is being changed with substrate Coordinate property, catalyzer carbon-carbon double bond that is preferential and substrate is made to carry out coordination, and not with C=O bond coordination, thus carry out asymmetric hydrogenation on carbon-carbon double bond.
2, the present invention take citral as substrate, adds certain additive, and chiral rhodium complex carries out asymmetric catalytic hydrogenation, thus obtains chirality geranial.Product yield is up to 99%, and enantioselectivity selectivity is up to 98%.
3, raw material of the present invention is easy to get, easy and simple to handle, mild condition; Additive therefor is simply inexpensive, and cost is lower; Product is easy to be separated, and yield is high, and enantioselectivity is high, is easy to industrialization scale operation.
Figure of description
Fig. 1 is the gas chromatogram of R-geranial product;
Fig. 2 is the gas chromatogram of S-geranial product;
Embodiment
Embodiment
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
In the following embodiments, the chirality rhodium complex that in following examples, coordination prepares rear use is expressed as [Rh (L*) (L)] X, also can by having the rhodium salt [Rh (L) of negatively charged ion and assistant ligand 2] X or [RhX (L)] 2synthesize with chiral ligand L* complexed in situ.
Gas chromatograph: Agilent7890, chromatographic column Supelco β-DEX tM225, injector temperature: 220 DEG C; Splitting ratio 50:1; Heating schedule: initial temperature 100 DEG C; Rise to 120 DEG C with the speed of 5 DEG C/min, keep 0min; Rise to 200 DEG C with the speed of 20 DEG C/min, keep 7min, detector temperature: 300 DEG C;
As shown in Figures 1 and 2, wherein, retention time 25.1min chromatographic peak is R-geranial; The chromatographic peak of retention time 24.6min is S-geranial.
In the present invention, rhodium salt used and chiral ligand etc. if no special instructions, are all bought by Reagent Company.As part: two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4,purchase from lark prestige science and technology, purity is 98wt%.
Embodiment one
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L1a (3.5mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added E formula citral (76.1mg, 0.50mmol are housed, E/Z=99/1, chirality rhodium complex [Rh (R-L1a) (COD)] BF 4be 1/100 with the mol ratio of citral) and sodium iodide (7.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 15 DEG C of stirring reactions 24 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 95%, S-enantiomeric excess value is 96%. 1HNMR(CDCl 3,400MHz):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment two
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands S-L1b (4.1mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL toluene solvant, this solution is added E formula citral (761mg, 5mmol are housed, E/Z=99/1, chirality rhodium complex [Rh (R-L1b) (COD)] BF 4be 1/1000 with the mol ratio of citral) and potassiumiodide (42mg, 0.25mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 35bar, 35 DEG C of stirring reactions 10 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 97%, R-enantiomeric excess value is 98%. 1HNMR(400MHz,CDCl 3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment three
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L1c (4.8mg, 0.005mmol) and two (2,5-norbornadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 20mL dichloromethane solvent, this solution is added Z formula citral (7.6g, 50mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L3c) (COD)] BF 4be 1/10000 with the mol ratio of citral) and tetrabutylammonium iodide (1.35g, 3.75mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 30bar, 30 DEG C of stirring reactions 18 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 93%, R-enantiomeric excess value is 96%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment four
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L1d (6.3mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, decompression pumps solvent and obtains brown solid, vacuum adds 50mL1 after taking out 2 hours, 2-dichloroethane solvent, this solution is added Z formula citral (38.1g is housed, 250mmol, E/Z=1/99, chirality rhodium complex [Rh (R-L3d) (COD)] BF 4be 1/50000 with the mol ratio of citral) and four n-octyl brometo de amonios (13.7g, 25mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 99%, R-enantiomeric excess value is 92%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment five
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L2a (3.1mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mLDMF solvent, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L2a) (COD)] BF 4be 1/100 with the mol ratio of citral) and ammonium iodide (7.2mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 80bar, 80 DEG C of stirring reactions 1 hour.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 87%, R-enantiomeric excess value is 87%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment six
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L2b (3.7mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL acetone solvent, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L2b) (COD)] BF 4be 1/100 with the mol ratio of citral) and four n-octyl ammonium iodides (59.4mg, 0.1mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 1bar ,-80 DEG C of stirring reactions 72 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 75%, R-enantiomeric excess value is 91%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment seven
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L2c (4.5mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL acetonitrile solvent, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L2c) (COD)] BF 4be 1/100 with the mol ratio of citral) and lithium iodide (10.1mg, 0.075mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 60bar, 70 DEG C of stirring reactions 2 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 93%, R-enantiomeric excess value is 82%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment eight
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L2d (6.0mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system by vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add Z formula citral (76.1mg, 0.5mmol, E/Z=1/99, chirality rhodium complex [Rh (R-L2d) (COD)] BF 4be 1/100 with the mol ratio of citral) and brometo de amonio (10.0mg, 0.1mmol), load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 5bar ,-40 DEG C of stirring reactions 48 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 92%, R-enantiomeric excess value is 83%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment nine
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L3a (3.1mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL ether solvent, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L2a) (COD)] BF 4be 1/100 with the mol ratio of citral) and phenyl triethylammonium ammonium iodide (15.3mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 45bar, 60 DEG C of stirring reactions 5 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 81%, R-enantiomeric excess value is 88%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment ten
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L3b (3.7mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4system by vacuum line, with nitrogen replacement 3 times, adds the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, adds 2mL tetrahydrofuran solvent, this solution is added Z formula citral (761mg is housed, 5mmol, E/Z=1/99, chirality rhodium complex [Rh (R-L2b) (COD)] BF 4be 1/1000 with the mol ratio of citral) and 4-hexyl iodide (241mg, 0.5mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 10bar, 0 DEG C of stirring reaction 36 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 82%, R-enantiomeric excess value is 83%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 11
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L3c (4.4mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L2c) (COD)] BF 4be 1/100 with the mol ratio of citral) and benzyltriethylammonium chloride (10.7mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 40bar, 45 DEG C of stirring reactions 8 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 81%, R-enantiomeric excess value is 83%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 12
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L3d (5.9mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL alcohol solvent, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L2d) (COD)] BF 4be 1/100 with the mol ratio of citral) and (ferrocenyl methyl) trimethylammonium ammonium iodide (19.3mg, in bottle 0.05mmol), load autoclave, after 6 hydrogen exchanges, initial hydrogen pressure is made to be 15bar, 10 DEG C of stirring reactions 30 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 90%, R-enantiomeric excess value is 81%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 13
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L4a (3.2mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L4a) (COD)] BF 4be 1/100 with the mol ratio of citral) and calcium iodide (14.7mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 94%, R-enantiomeric excess value is 87%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 14
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L4b (3.8mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L4b) (COD)] BF 4be 1/100 with the mol ratio of citral) and zinc iodide (16.0mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 92%, R-enantiomeric excess value is 84%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 15
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L4c (4.6mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L4c) (COD)] BF 4be 1/100 with the mol ratio of citral) and ethyl three n-propyl ammonium iodide (15.0mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 83%, R-enantiomeric excess value is 91%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 16
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L4d (6.0mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L4d) (COD)] BF 4be 1/100 with the mol ratio of citral) and (propyl group carbonic acyl radical sulphur ethyl) trimethylammonium ammonium iodide (15.9mg; in bottle 0.05mmol), load autoclave, after 6 hydrogen exchanges; initial hydrogen pressure is made to be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 92%, R-enantiomeric excess value is 83%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 17
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L5a (3.0mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L5a) (COD)] BF 4be 1/100 with the mol ratio of citral) and four n-heptyl ammonium iodides (26.9mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 75%, R-enantiomeric excess value is 91%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 18
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L5b (3.6mg, 0.005mmol) and (1,5-cyclooctadiene) rhodium chloride dimer [RCl (COD)] 2(2.5mg, 0.0025mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L5b) (COD)] BF 4be 1/100 with the mol ratio of citral) and 3-(trifluoromethyl) phenyl trimethicone ammonium iodide (16.6mg, in bottle 0.05mmol), load autoclave, after 6 hydrogen exchanges, initial hydrogen pressure is made to be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 82%, R-enantiomeric excess value is 91%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 19
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L5c (4.4mg, 0.005mmol) and two (1,5-cyclooctadiene) hexafluoro-antimonic acid rhodium [Rh (COD) 2] SbF 6(2.8mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L5c) (COD)] BF 4be 1/100 with the mol ratio of citral) and four n-heptyl brometo de amonios (24.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 92%, R-enantiomeric excess value is 91%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 20
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L5d (5.9mg, 0.005mmol) and two (1,5-cyclooctadiene) trifluoroacetic acid rhodium [Rh (COD) 2] OTf (2.3mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L5d) (COD)] BF 4be 1/100 with the mol ratio of citral) and 3-(trifluoromethyl) phenyltrimethylammonium bromide (14.2mg, in bottle 0.05mmol), load autoclave, after 6 hydrogen exchanges, initial hydrogen pressure is made to be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 89%, R-enantiomeric excess value is 78%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 21
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L6a (2.9mg, 0.005mmol) and two (1,5-cyclooctadiene) phosphofluoric acid rhodium [Rh (COD) 2] PF 6(2.3mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L6a) (COD)] BF 4be 1/100 with the mol ratio of citral) and ammonium chloride (2.7mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 83%, R-enantiomeric excess value is 75%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 22
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L6b (3.5mg, 0.005mmol) and two (2,5-norbornadiene) Tetrafluoroboric acid rhodium [Rh (NBD) 2] BF 4(2.3mg, 0.006mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L6b) (COD)] BF 4be 1/100 with the mol ratio of citral) and sodium iodide (7.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 91%, R-enantiomeric excess value is 77%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 23
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L6c (4.3mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.3mg, 0.0055mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L6c) (COD)] BF 4be 1/100 with the mol ratio of citral) and sodium iodide (7.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 77%, R-enantiomeric excess value is 78%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 24
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L6d (5.8mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L6d) (COD)] BF 4be 1/100 with the mol ratio of citral) and sodium iodide (7.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 92%, R-enantiomeric excess value is 80%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 25
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L7 (1.9mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L7) (COD)] BF 4be 1/100 with the mol ratio of citral) and sodium iodide (7.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 40bar, 60 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 72%, R-enantiomeric excess value is 78%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 26
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L8 (2.2mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 20mL isopropanol solvent, this solution is added Z formula citral (15.2g, 100mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L8) (COD)] BF 4be 1/20000 with the mol ratio of citral) and four hexyl brometo de amonios (2.1g, 10mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 30bar, 30 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 97%, R-enantiomeric excess value is 92%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 27
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L9 (2.8mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L9) (COD)] BF 4be 1/100 with the mol ratio of citral) and sodium iodide (7.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 10bar, 0 DEG C of stirring reaction 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 78%, R-enantiomeric excess value is 77%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 28
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L10 (2.4mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L10) (COD)] BF 4be 1/100 with the mol ratio of citral) and sodium iodide (7.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 60bar, 25 DEG C of stirring reactions 48 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 77%, R-enantiomeric excess value is 79%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 29
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L11 (2.6mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL trifluoroethanol solvent, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L11) (COD)] BF 4be 1/100 with the mol ratio of citral) and four n-heptyl ammonium chlorides (16.7mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 1bar, 80 DEG C of stirring reactions 36 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 93%, R-enantiomeric excess value is 95%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 30
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L12 (3.4mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L12) (COD)] BF 4be 1/100 with the mol ratio of citral) and sodium iodide (7.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 10bar, 60 DEG C of stirring reactions 10 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 78%, R-enantiomeric excess value is 92%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 31
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L13 (3.5mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L13) (COD)] BF 4be 1/100 with the mol ratio of citral) and sodium iodide (7.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 30bar ,-78 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 91%, R-enantiomeric excess value is 80%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 32
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L14 (4.5mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL isopropanol solvent, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L14) (COD)] BF 4be 1/100 with the mol ratio of citral) and four hexyl ammonium chlorides (8.3mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 86%, R-enantiomeric excess value is 82%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 33
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L15 (3.6mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL trifluoroethanol solvent, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L15) (COD)] BF 4be 1/100 with the mol ratio of citral) and four hexyl brometo de amonios (10.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 10bar ,-40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 75%, R-enantiomeric excess value is 79%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 34
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L16 (3.7mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L16) (COD)] BF 4be 1/100 with the mol ratio of citral) and sodium iodide (7.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 20bar, 40 DEG C of stirring reactions 16 hours.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 71%, R-enantiomeric excess value is 81%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 35
The preparation of chirality geranial
In a 10mL reaction tubes, add Phosphine ligands R-L17 (4.6mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L17) (COD)] BF 4be 1/100 with the mol ratio of citral) and sodium iodide (7.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 60bar, 30 DEG C of stirring reactions 1 hour.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 86%, R-enantiomeric excess value is 72%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Embodiment 36
The preparation of chirality geranial
In a 10mL reaction tubes, add chiral rhodium complex [Rh (R-L17) (COD)] BF 4(6.2mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mL methanol solvate, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (R-L17) (COD)] BF 4be 1/100 with the mol ratio of citral) and sodium iodide (7.5mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 60bar, 30 DEG C of stirring reactions 1 hour.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product.Productive rate is 73%, R-enantiomeric excess value is 75%. 1HNMR(400MHz,CDCl3):δ0.95(d,J＝6.6Hz,3H),1.30-1.39(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.08(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。
Comparative example
In a 10mL reaction tubes, add racemization Phosphine ligands L2a (3.1mg, 0.005mmol) and two (1,5-cyclooctadiene) Tetrafluoroboric acid rhodium [Rh (COD) 2] BF 4(2.1mg, 0.005mmol), system passes through vacuum line, with nitrogen replacement 3 times, add the new degassed toluene (2mL) steamed, solution at room temperature stirs 1 hour, and decompression pumps solvent and obtains brown solid, after vacuum takes out 2 hours, add 2mLDMF solvent, this solution is added Z formula citral (76.1mg, 0.5mmol are housed, E/Z=1/99, chirality rhodium complex [Rh (L2a) (COD)] BF 4be 1/100 with the mol ratio of citral) and ammonium iodide (7.2mg, 0.05mmol) bottle in, load autoclave, after 6 hydrogen exchanges, make initial hydrogen pressure be 80bar, 80 DEG C of stirring reactions 1 hour.Cooling, carefully releases gas, opens autoclave, and take out bottle, drain solvent, NMR detects transformation efficiency, gas-chromatography (chromatographic column β-DEX tM225) detect enantiomeric excess, column chromatography obtains product, is raceme after testing.Productive rate is 79%. 1HNMR(400MHz,CDCl3):δ0.94(d,J＝6.6Hz,3H),1.30-1.38(m,2H,),1.68(s,3H),1.99(s,3H),1.98-2.06(m,3H),2.24(dd,J＝7.8,2.6Hz,1H),2.37(dd,J＝5.4,1.6Hz,1H),5.05(t,J＝7.0Hz,1H),9.77(s,1H)。

Claims (10)

1. prepared a method for chirality geranial by citral asymmetric catalytic hydrogenation, it is characterized in that, under the effect of chirality rhodium complex catalyst and additive, asymmetric hydrogenation is carried out to citral, preparation R or S chirality geranial.
2. method according to claim 1, is characterized in that, described additive is the one or two or more in iodide, bromide and muriate.
3. method according to claim 2, it is characterized in that, described iodide are the one or two or more in sodium iodide, potassiumiodide, ammonium iodide, calcium iodide, zinc iodide, lithium iodide, tetrabutylammonium iodide, phenyl triethylammonium ammonium iodide, (ferrocenyl methyl) trimethylammonium ammonium iodide, ethyl three n-propyl ammonium iodide, four n-octyl ammonium iodides, (propyl group carbonic acyl radical sulphur ethyl) trimethylammonium ammonium iodide, 4-hexyl iodide, four n-heptyl ammonium iodides and 3-(trifluoromethyl) phenyl trimethicone ammonium iodide; Described bromide is the one or two or more in brometo de amonio, phenyl triethylammonium brometo de amonio, (ferrocenyl methyl) trimethylammonium bromide, ethyl three n-propyl brometo de amonio, four n-octyl brometo de amonios, (propyl group carbonic acyl radical sulphur ethyl) trimethylammonium bromide, four hexyl brometo de amonios, four n-heptyl brometo de amonios and 3-(trifluoromethyl) phenyltrimethylammonium bromide; Described muriate is the one or two or more in ammonium chloride, benzyltriethylammonium chloride, (ferrocenyl methyl) trimethyl ammonium chloride, ethyl three n-propyl ammonium chloride, four n-octyl ammonium chlorides, (propyl group carbonic acyl radical sulphur ethyl) trimethyl ammonium chloride, four hexyl ammonium chlorides, four n-heptyl ammonium chlorides or 3-(trifluoromethyl) phenyl trimethicone ammonium chloride; Described additive is preferably the one or two or more in sodium iodide, potassiumiodide, tetrabutylammonium iodide, phenyl triethylammonium ammonium iodide, (ferrocenyl methyl) trimethylammonium ammonium iodide, 4-hexyl iodide, four n-octyl brometo de amonios, four hexyl brometo de amonios, benzyltriethylammonium chloride and four hexyl ammonium chlorides; Be more preferably the one or two or more in sodium iodide, potassiumiodide, tetrabutylammonium iodide, four n-octyl brometo de amonios, four hexyl brometo de amonios, four hexyl ammonium chlorides and benzyltriethylammonium chloride; One or two or more more preferably in sodium iodide, tetrabutylammonium iodide, four n-octyl brometo de amonios and benzyltriethylammonium chloride.
4. the method according to claim 1 or 2 or 3, is characterized in that, the mol ratio of described additive and citral is 1:1 ~ 20, is preferably 1:5 ~ 10.
5. method according to claim 1, is characterized in that, described chirality rhodium complex is formed by the rhodium salt and chiral ligand coordination with negatively charged ion and assistant ligand; The structural formula of described chirality rhodium complex is [Rh (L*) (L)] X, and the structural formula with the rhodium salt of negatively charged ion and assistant ligand is [Rh (L) 2] X or [RhX (L)] 2, wherein, L* is chiral ligand, and L is assistant ligand, and X is negatively charged ion.
6. method according to claim 5, is characterized in that, described chiral ligand L* is any one part be selected from L1 ~ L17, and wherein, the configuration of ligand L 1 ~ L6 is that the structure of R or S, L1 ~ L17 is as follows:
Described chiral ligand is preferably L1 ~ L4, L7 ~ L11, L12 or L15, is more preferably L1, L3, L8, L11, L14 or L15, more preferably L1, L8 or L11, and wherein, Ar represents a:C respectively 6h 5, b:4-CH 3oC 6h 4, c:4-CF 3c 6h 4or d:3,5-di-tBu-4-MeOC 6h 2.
7. method according to claim 5, is characterized in that, described in the negatively charged ion X had in the rhodium salt of negatively charged ion and assistant ligand be Cl -, BF 4 -, SbF 6 -, CF 3cOO -or PF 6 -, be preferably BF 4 -, SbF 6 -or PF 6 -, more preferably BF 4 -or SbF 6 -; Described assistant ligand L is diene, is preferably pungent two rare or 2, the 5-norbornadienes of 1,5-ring.
8. method according to claim 1 or 5, it is characterized in that, the mol ratio of described chirality rhodium complex and citral is 1:100 ~ 100000, is preferably 1:1000 ~ 50000, is more preferably 1:10000 ~ 50000.
9. method according to claim 1, is characterized in that, described asymmetric hydrogenation carries out having under solvent or solvent-free condition, and described solvent is the one or two or more in the polar solvent of non-alkane, non-polar solvent or protic solvent; Described polar solvent is preferably the one or two or more in methylene dichloride, 1,2-ethylene dichloride, DMF, acetone and acetonitrile; Non-polar solvent is preferably the one or two or more in toluene, ether and tetrahydrofuran (THF); Described protic solvent is preferably the one or two or more in methyl alcohol, ethanol, Virahol and trifluoroethanol; Described solvent is more preferably the one or two or more in toluene, methylene dichloride, 1,2-ethylene dichloride, ether, tetrahydrofuran (THF), methyl alcohol, ethanol, Virahol and trifluoroethanol.
10. method according to claim 1, is characterized in that, the gauge pressure of the nitrogen atmosphere of described asyininetric hydrogenation is 1 ~ 80bar, is preferably 10-45bar, is more preferably 20-35bar; Temperature of reaction is-80 DEG C ~ 80 DEG C, is preferably 0-60 DEG C, is more preferably 15-35 DEG C; Reaction times is 1 ~ 72 hour, is preferably 5-36 hour, is more preferably 10-24 hour.
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CN106086089A (en) * 2016-06-17 2016-11-09 浙江工业大学 A kind of method that enzyme process asymmetric reduction citral improves (R) citronellal optical purity
CN108794314A (en) * 2017-04-28 2018-11-13 山东新和成药业有限公司 A kind of method of citral hydrogenation synthesis citronellal
CN110963889A (en) * 2019-12-13 2020-04-07 万华化学集团股份有限公司 Method for synthesizing left-optical-activity citronellol by asymmetric hydrosilylation of citral
CN111718250A (en) * 2020-06-28 2020-09-29 万华化学集团股份有限公司 Method for preparing R-citronellal

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CN101675020A (en) * 2007-04-25 2010-03-17 巴斯夫欧洲公司 Method for synthesizing optically active carbonyl compounds
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US4237072A (en) * 1977-07-04 1980-12-02 Rhone-Poulenc Industries Preparation of optically active citronellal
CN101039894A (en) * 2004-10-11 2007-09-19 巴斯福股份公司 Method for the production of optically active carbonyl compounds
CN101675020A (en) * 2007-04-25 2010-03-17 巴斯夫欧洲公司 Method for synthesizing optically active carbonyl compounds
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106086089A (en) * 2016-06-17 2016-11-09 浙江工业大学 A kind of method that enzyme process asymmetric reduction citral improves (R) citronellal optical purity
CN106086089B (en) * 2016-06-17 2019-10-29 浙江工业大学 A kind of method that enzyme process asymmetric reduction citral improves (R)-citronellal optical purity
CN108794314A (en) * 2017-04-28 2018-11-13 山东新和成药业有限公司 A kind of method of citral hydrogenation synthesis citronellal
CN110963889A (en) * 2019-12-13 2020-04-07 万华化学集团股份有限公司 Method for synthesizing left-optical-activity citronellol by asymmetric hydrosilylation of citral
CN110963889B (en) * 2019-12-13 2022-07-12 万华化学集团股份有限公司 Method for synthesizing left-optical-activity citronellol by asymmetric hydrosilylation of citral
CN111718250A (en) * 2020-06-28 2020-09-29 万华化学集团股份有限公司 Method for preparing R-citronellal
CN111718250B (en) * 2020-06-28 2022-04-22 万华化学集团股份有限公司 Method for preparing R-citronellal

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