CN114436831A - Synthesis method of chiral 1-phenylpropyl acetate compound - Google Patents

Synthesis method of chiral 1-phenylpropyl acetate compound Download PDF

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CN114436831A
CN114436831A CN202011203559.6A CN202011203559A CN114436831A CN 114436831 A CN114436831 A CN 114436831A CN 202011203559 A CN202011203559 A CN 202011203559A CN 114436831 A CN114436831 A CN 114436831A
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chiral
phenylpropyl
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胡向平
董超
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Zhongke New Catalytic Technology Dalian Co ltd
Dalian Institute of Chemical Physics of CAS
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Zhongke New Catalytic Technology Dalian Co ltd
Dalian Institute of Chemical Physics of CAS
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Abstract

The invention provides a method for synthesizing a chiral 1-phenylpropyl acetate compound. The method takes 1-phenylpropyl-1-en-1-yl acetate compounds and hydrogen as raw materials, and prepares the chiral 1-phenylpropyl acetate compounds with high yield and high enantioselectivity under the catalysis of chiral rhodium catalysts. Wherein the chiral rhodium catalyst is prepared by the rhodium salt catalyst precursor and the chiral ferrocenyl phosphine-phosphoramidite ligand in situ. The catalytic reaction needs to be carried out at P (H)2) At a pressure of 20barThe reaction is carried out at room temperature by using 1, 2-dichloroethane and tert-butanol as mixed solvent. The catalytic reaction has the characteristics of mild conditions, simple and convenient operation, cheap and easily obtained substrate, excellent stereoselectivity, high yield and the like.

Description

Synthesis method of chiral 1-phenylpropyl acetate compound
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a synthetic method of a chiral 1-phenylpropyl acetate compound.
Background
The chiral ester structure widely exists in medicines, pesticides, perfumes and natural products, and in addition, the hydrolysis reaction of the chiral ester under the alkaline condition is one of the simplest and most effective methods for preparing the chiral alcohol, and the chiral alcohol has high reaction activity and is an important medical intermediate. Therefore, the efficient and high-stereoselectivity construction of structurally diverse chiral ester structural compounds is always the leading and challenging subject of organic synthetic chemistry and asymmetric catalytic research. The construction of chiral ester structures by asymmetric catalytic hydrogenation of unsaturated alkenyl esters is one of the most straightforward and efficient methods. Over the last two decades, this asymmetric catalytic hydrogenation process has made significant progress: 1) a number of highly efficient chiral metal and organic catalyst systems have been discovered; 2) the range of unsaturated alkenyl ester raw materials for directly preparing chiral ester is greatly expanded; 3) are widely used in the synthesis of pharmaceuticals and natural products (d.j.age, a.h.m.de Vries, j.g.de Vries, Asymmetric Homogneous hydrogenetics at scale, chem.soc.rev.,2012,41, 3340; T.M.Konrad, P.Schmitts, W.Leitner, G.Franci Oma, high enzymic Selective Rh-catalytic Hydrogenation of 1-Alkyl Vinyl Esters Using phosphoric-phosphoric acid ligands, chem.Eur.J.,2013,19, 13299; etayo, A.Vidal-Ferran, Rhodium-catalyzed asymmetry as a variable Synthetic tool for the Preparation of chiral drugs, chem.Soc.Rev.,2013,42, 728; H.Fern-ndez-P é rez, J.Benet-Buchholz, A.Vidal-Ferran, Enantiopure Narrow bit-Angle P-OP Ligands Synthesis and catalysis Performance in asymmetry Hydroformation and hydroformation, chem.Eur.J.,2014,20, 15375; T.Hammerer, W.Leitner, G.Franci oa, Synthesis of phosphor-phosphor oxides and the Application in asymmetry catalyst chemistry. ChemCat chem.2015, 7, 1583; schmitz, K.Houshusen, W.Leitner, G.Franci oa, Bidensate Phospholine-Phosphoramite Ligands of the Bettips Family for Rh-catalyst equipped asymmetry production.Acs.Catalyd, 2016,6, 1584; H.Fern-ndez-Perrez, B.Balakrishna, A.Vidal-Ferran, Structural investments on Enantiopure P-OP Ligands, A High Performance P-OP Ligands for Rhodium-catalysis hydroformations, chem.Eur.J.,2018,13, 1525; ). Therefore, the development of an efficient novel chiral catalyst system and the realization of the catalytic asymmetric hydrogenation reaction with the participation of the 1-phenylprop-1-en-1-yl acetate compounds with wide substrate application range and high regioselectivity have positive significance for constructing chiral ester (alcohol) structures with various structures, expanding the application range of the asymmetric hydrogenation reaction catalyzed by the rhodium salt-chiral ferrocenylphosphine-phosphoramidite ligand catalyst and the like.
Disclosure of Invention
The invention aims to provide a method for synthesizing a chiral 1-phenylpropyl acetate compound by asymmetric hydrogenation of a rhodium-catalyzed 1-phenylpropyl-1-en-1-yl acetate compound. The method has the characteristics of easily obtained raw materials, simple operation, mild reaction conditions, high enantioselectivity and the like.
The invention provides a catalytic asymmetric synthesis method of a chiral 1-phenylpropyl acetate compound. Under the catalysis of a chiral rhodium catalyst generated by a rhodium salt catalyst precursor and a chiral ferrocenyl phosphine-phosphoramidite ligand in situ, the chiral 1-phenylpropyl acetate compound is synthesized by the asymmetric hydrogenation reaction of the 1-phenylpropyl-1-en-1-yl acetate compound with high yield and high enantioselectivity.
The chiral rhodium catalyst is prepared by stirring a rhodium salt catalyst precursor and a chiral ferrocenyl phosphine-phosphoramidite ligand in a reaction medium for 0.5-2 hours in a molar ratio of 1.0: 0.5-5.0 in situ under the protection of nitrogen. The rhodium salt catalyst precursor and the chiral ferrocenylphosphine-phosphoramidite ligand are preferably present in a molar ratio of 1.0: 1.1.
The molar ratio of the chiral rhodium salt catalyst precursor to the chiral ferrocenylphosphine-phosphoramidite ligand to the 1-phenylpropan-1-en-1-yl acetate compound is 1.0: 0.5-5.0: 10-100.
The molar ratio of the chiral rhodium catalyst to the 1-phenylpropane-1-en-1-yl acetate compound in the reaction medium is 1:10 to 100.
The catalytic reaction conditions are as follows:
temperature: -40 ℃ to 50 ℃, preferably room temperature;
pressure: p (H)2) 1-100bar, preferably 20 bar;
time: 0.5 to 24 hours, preferably 24 hours.
Reaction medium: 1, 2-dichloroethane (2ml) + tert-butanol (1. mu.L-100. mu.L), preferably 1, 2-dichloroethane (2ml) + tert-butanol (50. mu.L).
The method comprises the following specific steps:
(1) preparation of chiral rhodium catalyst: under the protection of nitrogen gas, [ Rh (COD) ]2]BF4Stirring the obtained product and a chiral ferrocenylphosphine-phosphoramidite ligand in a molar ratio of 1: 0.5-5.0 for 0.5-2 hours in a reaction medium to prepare a chiral rhodium catalyst;
(2) preparing a chiral 1-phenylpropyl acetate compound: under the protection of nitrogen gas, [ Rh (COD) ]2]BF4Stirring the chiral ferrocenylphosphine-phosphoramidite ligand and a chiral ferrocenylphosphine-phosphoramidite ligand in an in-situ preparation manner in a reaction medium according to a molar ratio of 1: 0.5-5.0 for 0.5-2 hours to prepare a chiral rhodium catalyst, transferring the chiral rhodium catalyst solution to an ampoule bottle filled with a 1-phenylpropan-1-en-1-yl acetate compound, adding 1 mu L-100 mu L of tert-butyl alcohol by using a microsyringe, putting the ampoule bottle into a reaction kettle, and maintaining the hydrogen pressure of the reaction kettle at 1-100bar after replacing for three times by hydrogen; stirring for 12-24 hours at room temperature; after the reaction is finished, carrying out reduced pressure rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain the chiral 1-phenylpropyl acetate compound; wherein the dosage of the chiral rhodium catalyst is 1 mol%;
the reaction medium is one or more than two of methanol, ethanol, isopropanol, n-propanol, tert-butanol, trifluoroethanol, acetic acid or dichloromethane, 1, 2-dichloroethane, tetrahydrofuran, benzene and toluene, preferably 1, 2-dichloroethane and tert-butanol. The chiral 1-phenylpropyl acetate compound has the following structure I or II:
Figure BDA0002756270050000041
in the formula, I and II are enantiomers of each other.
In the formula: r1、R2、R3Is one or two of C1-C40 alkyl, C3-C12 cycloalkyl, C3-C12 cycloalkyl with substituent, aryl, substituted aryl, benzyl, substituted benzyl, heterocyclic aryl and substituted heterocyclic aryl; the substituents on the C3-C12 cycloalkyl, aryl, benzyl and heteroaromatic groups are C1-C40 alkyl, C1-C40, one or more than two of alkoxy, halogen, nitro, ester group or cyano.
The 1-phenylprop-1-en-1-yl acetate has the following structure III:
Figure BDA0002756270050000042
in the formula: r is1、R2、R3With R in the formula I or II1、R2、R3Are equivalent groups.
The rhodium salt catalyst precursor is [ Rh (COD) ]2]BF4、[Rh(CO)2(acac)]、[Rh(COD)Cl]2、[Rh(COD)2]OTf、[Rh(C2H4)2Cl]2、[Rh(OAc)2]Preferably [ Rh (COD) ]2]BF4。
The chiral ferrocenylphosphine-phosphoramidite ligand has the following structure V or VI:
Figure BDA0002756270050000043
in the formula (S)c,Rp,Sa) -IV and (R)c,Sp,Ra) -V are enantiomers of each other.
In the formula: ar is phenyl and substituted phenyl, naphthyl and substituted naphthyl, and contains one or more than two five-membered or six-membered heterocyclic aromatic groups of oxygen, sulfur and nitrogen atoms; the substituent on the substituted phenyl or the substituted naphthyl is one or more than two of C1-C40 alkyl, C1-C40 alkoxy, halogen, nitro, ester group or cyano, and the number of the substituent is 1-5; r4、R5Is one or two of C1-C40 alkyl, C3-C12 cycloalkyl, phenyl and substituted phenyl, five-membered or six-membered heterocyclic aromatic group containing one or more than two oxygen, sulfur and nitrogen atoms, benzyl and substituted benzyl, naphthyl and substituted naphthyl; the substituents on the phenyl, benzyl and naphthyl groups are C1-C40 alkyl and C1-C40 alkylOne or more of oxy, halogen, nitro, ester or cyano.
The catalytic reaction conditions are preferably as follows:
temperature: room temperature;
reaction medium: 1, 2-dichloroethane (2ml) + tert-butanol (50. mu.L).
Pressure: p (H)2)＝20bar；
Time: for 24 hours.
The mol ratio of the rhodium salt catalyst precursor, the chiral ferrocenyl phosphine-phosphoramidite ligand and the 1-phenylprop-1-en-1-yl acetate compound III is preferably 1:1.1: 100;
the volume ratio of the reaction solvent 1, 2-dichloroethane to tert-butanol is preferably 40: 1;
the reaction equation of the invention is as follows:
Figure BDA0002756270050000051
the invention has the following advantages:
1. the substrate has good applicability, and can obtain good results for various substituted 1-phenyl propenyl acetate compounds III.
2. Good reaction activity, excellent regioselectivity and high diastereoselectivity and enantioselectivity.
3. The reaction condition is mild, and the substrate is cheap and easy to obtain.
4. The chiral catalyst is simple and convenient to prepare and low in dosage. The chiral ligand is simple to synthesize, and the initial raw material is cheap and easy to obtain.
Drawings
FIG. 1 is a NMR hydrogen spectrum of phenylpropyl (S) -1-acetate I-1 prepared in example 1;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of (S) -1-phenylpropyl acetate I-1 prepared in example 1;
FIG. 3 is a NMR spectrum of propyl (S) -1- (4-methoxyphenyl) acetate I-2 prepared in example 19;
FIG. 4 is a NMR carbon spectrum of propyl (S) -1- (4-methoxyphenyl) acetate I-2 prepared in example 19;
FIG. 5 is a NMR spectrum of propyl (S) -1- (4-chlorophenyl) acetate I-3 prepared in example 20;
FIG. 6 is a carbon nuclear magnetic resonance spectrum of propyl (S) -1- (4-chlorophenyl) acetate I-3 prepared in example 20;
FIG. 7 is a NMR hydrogen spectrum of propyl (S) -1- (3-methylphenyl) acetate I-4 prepared in example 21;
FIG. 8 is a NMR carbon spectrum of propyl (S) -1- (3-methylphenyl) acetate I-4 prepared in example 21;
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto. NMR was measured by Bruker400 NMR and Gas Chromatography (GC) by Agilent 7890A.
Asymmetric hydrogenation reaction
Example 1: under the protection of nitrogen gas, [ Rh (COD) ]2]BF4(0.00125mmol,1 mol%), chiral ferrocenylphosphine-phosphoramidite ligand (0.001375mmol,1.1 mol%) was dissolved in 1, 2-dichloroethane (1.0mL), stirred at room temperature (25 ℃ C.) for 1 hour, a solution of the substrate 1-phenylpropenylacetate (0.125mmol) in 1, 2-dichloroethane (1.0mL) and 50. mu.L of t-butanol were added, and the mixture was placed in an autoclave, replaced with hydrogen 3 times, and then reacted at room temperature (25 ℃ C.) for 24 hours with 20bar of hydrogen. Slowly releasing hydrogen, removing the solvent, and separating by using a silica gel column to obtain the chiral 1-phenylpropyl acetate I-1. Conversion 99%, 91% ee water determined by Chiral GC (HP-Chiral-20B 30m × 0.250mm, T ═ 105 ℃,1.5 mL/min); t is tR(minor)23.99min,tR(major)24.68min；[α]D 25＝25.3(c＝2.46,CHCl3)；1H NMR(400MHz,CDCl3)δ7.36–7.26(m,5H),5.68–5.65(t,J＝6.9Hz,1H),2.07(s,3H),1.98–1.87(m,1H),1.86–1.76(m,1H),0.90–0.86(t,J＝7.4Hz,3H)；13C NMR(101MHz,CDCl3) Delta 170.5,140.6,128.4,127.8,126.6,29.3,21.3,9.9 nuclear magnetic resonance hydrogen spectrum and carbon spectrum of the product I-1 are shown in figure 1 and figure 2.
Ⅲ-1，I-1，(Sc,Rp,Sa)-IV-The structural formula of 1 is as follows:
Figure BDA0002756270050000071
example 2: (S)c,Rp,Sa) Reaction of-IV-2 as ligand to form product I-1
The ligand (S) in example 1 is addedc,Rp,Sa) Ligand (S) for-IV-1c,Rp,Sa) Example 1 was repeated except that-IV-2 was used. The reaction gave compound I-1 in 99% yield and 82% ee.
(Sc,Rp,Sa) The structural formula of-IV-2 is as follows:
Figure BDA0002756270050000072
example 3: (S)c,Rp,Sa) Reaction of-IV-3 as ligand to form the product I-1
The ligand (S) in example 1c,Rp,Sa) Ligand (S) for-IV-1c,Rp,Sa) Example 1 was repeated except for-IV-3. The reaction gave compound I-1 in 99% yield and 83% ee.
(Sc,Rp,Sa) The structural formula of-IV-3 is as follows:
Figure BDA0002756270050000081
example 4: (S)c,Rp,Sa) Reaction of-IV-4 as ligand to give the product I-1
The ligand (S) in example 1c,Rp,Sa) Ligand (S) for-IV-1c,Rp,Sa) Example 1 was repeated in place of example 4. The reaction gave compound I-1 in 99% yield and 57% ee.
(Sc,Rp,Sa) The structural formula of-IV-4 is as follows:
Figure BDA0002756270050000082
example 5: (R)c,Sp,Ra) Reaction of-IV-5 as ligand to give the product I-1
The ligand (S) in example 1 is addedc,Rp,Sa) Ligand (R) for-IV-1c,Sp,Ra) Example 1 was repeated except for-IV-5. The reaction gave compound I-1 in 99% yield and-85% ee.
(Rc,Sp,Ra) The structural formula of-IV-5 is as follows:
Figure BDA0002756270050000083
example 6: (R)c,Sp,Ra) Reaction of-IV-6 as ligand to give the product I-1
The ligand (S) in example 1 is addedc,Rp,Sa) Ligand (R) for-IV-1c,Sp,Ra) Example 1 was repeated except for-IV-6. The reaction gave compound I-1 in 99% yield, -75% ee.
(Rc,Sp,Ra) The structural formula of-IV-6 is as follows:
Figure BDA0002756270050000091
example 7: [ Rh (CO) ]2(acac)]Formation of product I-1 as catalyst precursor
Example 1 [ Rh (COD) ]2]BF4With [ Rh (CO) ]2(acac)]Instead, the rest is the same as example 1. Compound I-1 was obtained in 70% yield, 25% ee.
Example 8: [ Rh (COD) Cl]2Formation of product I-1 as catalyst precursor
Example 1 [ Rh (COD) ]2]BF4With [ Rh (COD) Cl]2Instead of the formerOtherwise, the same procedure as in example 1 was repeated. Compound I-1 was obtained in 50% yield, 17% ee.
Example 9: anhydrous tetrahydrofuran as solvent to produce the product I-1
The same procedure used in example 1 was repeated except for replacing 1, 2-dichloroethane in example 1 with anhydrous tetrahydrofuran to give compound I-1 in 65% yield and 70% ee.
Example 10: dichloromethane is used as solvent to react to generate the product I-1
The same procedure used in example 1 was repeated except for replacing 1, 2-dichloroethane in example 1 with dichloromethane to give compound I-1 in 99% yield and 83% ee.
Example 11: trifluoroethanol is used as a solvent to react to generate a product I-1
The same procedure used in example 1 was repeated except for replacing 1, 2-dichloroethane in example 1 with trifluoroethanol to give compound I-1 in 50% yield and 17% ee.
Example 12: methanol is used as an additive to generate a product I-1
The procedure of example 1 was repeated except that the tert-butanol in example 1 was replaced with methanol. The reaction gave compound I-1 in 90% yield and 80% ee.
Example 13: acetic acid as an additive to produce product I-1
The procedure of example 1 was repeated except that the tert-butanol in example 1 was replaced with acetic acid. The reaction gave compound I-1 in 99% yield, 81% ee.
Example 14: the reaction without tert-butyl alcohol produces the product I-1
The same procedure used in example 1 was repeated except that tert-butanol was not added in example 1 to give compound I-1 in 99% yield and 85% ee.
Example 15: reaction at 0 deg.C to produce product I-1
The same procedure as in example 1 was repeated except for replacing the reaction temperature in example 1 with 0 ℃ to give compound I-1 in 90% yield and 81% ee.
Example 16: reacting at 50 ℃ to generate a product I-1
The reaction temperature in example 1 was replaced with 50 ℃ and the rest of example 1 gave compound I-1 in 99% yield and 35% ee.
Example 17: 10bar reaction to give the product I-1
The reaction pressure in example 1 was replaced by 10bar, and the remainder of the procedure was the same as in example 1, yielding compound I-1 in 99% yield and 80% ee.
Example 18: reaction at 30bar gave the product I-1
The reaction pressure in example 1 was replaced with 30bar, the rest of the same being as in example 1, giving compound I-1 in 99% yield, 83% ee.
Example 19: III-2 reaction as substrate to give the product propyl (S) -1- (4-methoxyphenyl) acetate I-2 the substrate III-1 from example 1 was replaced by the substrate III-2 from the rest of example 1. The reaction gave compound I-2 in 99% yield and 94% ee. The nuclear magnetic resonance hydrogen spectrum and the carbon spectrum of the product I-2 are shown in figures 3 and 4: 94% ee was determined by Chiral GC (HP-Chiral-20B 30 m.times.0.250 mm, T ═ 110 ℃,0.5 mL/min); t is tR(minor)107.01min,tR(major)109.22min；[α]D 25＝8.7(c＝3.05,CHCl3)；1H NMR(400MHz,CDCl3)δ7.28–7.24(m,1H),6.89–6.85(m,1H),5.63–5.60(m,1H),3.79(s,3H),2.04(s,3H),1.95–1.88(m,1H),1.84–1.73(m,1H),0.86–0.84(t,J＝7.4Hz,1H)；13C NMR(101MHz,CDCl3)δ170.5,159.2,132.6,128.0,113.8,77.1,55.2,29.1,21.3,10.0.
The structural formula of III-2 and I-2 is as follows:
Figure BDA0002756270050000111
example 20: III-3 is used as a substrate to react to generate a product (S) -1- (4-chlorphenyl) propyl acetate I-3
The substrate III-1 in example 1 was replaced with the substrate III-3 in the rest of example 1. The reaction gave compound I-3 in 99% yield and 95% ee. The NMR spectrum and the carbon spectrum of the product I-3 are shown in FIGS. 5 and 6: 95% ee was determined by Chiral GC (HP-Chiral-20B 30 m.times.0.250 mm, T ═ 115 ℃ C., 1 mL/min); t is tR(minor)48.62min,tR(major)49.49min；[α]D 25＝62.0(c＝1.77,CHCl3)；1H NMR(400MHz,CDCl3)δ7.32–7.24(m,4H),5.63–5.60(t,J＝6.9Hz,1H),2.07(s,3H),1.93–1.86(m,1H),1.81–1.74(m,1H),0.89–0.85(t,J＝7.4Hz,3H)；13C NMR(101MHz,CDCl3)δ170.3,139.1,133.6,128.6,128.0,76.8,29.2,21.2,9.8.
The structural formula of III-3 and I-3 is as follows:
Figure BDA0002756270050000112
example 21: III-4 as a substrate to generate the product (S) -1- (3-methylphenyl) propyl acetate I-4
The substrate III-1 in example 1 was replaced with the substrate III-4 in the rest of example 1. The reaction gave compound I-4 in 99% yield and 90% ee. The NMR spectrum and the carbon spectrum of the product I-4 are shown in FIGS. 7 and 8: 90% ee was determined by Chiral GC (HP-Chiral-20B 30 m.times.0.250 mm, T.105 ℃,1.5 mL/min.); t is tR(minor)41.66min,tR(major)42.85min；[α]D 25＝35.9(c＝0.78,CHCl3)；1HNMR(400MHz,CDCl3)δ7.23–7.21(d,J＝8.0Hz,2H),7.15–7.13(d,J＝7.8Hz,2H),5.64–5.61(t,J＝6.9Hz,1H),2.33(s,3H),2.06(s,3H),1.97–1.86(m,1H),1.85–1.74(m,1H),0.89–0.85(t,J＝7.4Hz,3H)；13C NMR(101MHz,CDCl3) Delta 170.5,140.5,138.0,128.6,128.3,127.3,123.6,77.4,29.3,21.5,21.3,10.0. III-4, I-4 has the following structural formula:
Figure BDA0002756270050000121

Claims (10)

1. a method for synthesizing chiral 1-phenylpropyl acetate compounds is characterized by comprising the following steps: the method takes 1-phenylpropyl-1-en-1-yl acetate compounds and hydrogen as raw materials, and chiral 1-phenylpropyl acetate compounds are synthesized by asymmetric hydrogenation reaction under the action of a chiral rhodium catalyst.
2. The method for synthesizing the chiral 1-phenylpropyl acetate compound according to claim 1, wherein:
the chiral 1-phenylpropyl acetate has the following structure I or II:
Figure FDA0002756270040000011
in the formula, I and II are enantiomers of each other;
in the formula: r1、R2、R3Is one or two of C1-C40 alkyl, C3-C12 cycloalkyl, C3-C12 cycloalkyl with substituent, aryl, substituted aryl, benzyl, substituted benzyl, heterocyclic aromatic group and substituted heterocyclic aromatic group; the substituents on the C3-C12 naphthenic base, aryl, benzyl and heterocyclic aromatic base are one or more than two of C1-C40 alkyl, C1-C40 alkoxy, halogen, nitro, ester or cyano.
3. The method for synthesizing the chiral 1-phenylpropyl acetate compound according to claim 1, wherein:
the 1-phenylprop-1-en-1-yl acetate compound has the following structure III:
Figure FDA0002756270040000012
4. the method for synthesizing the chiral 1-phenylpropyl acetate compound according to claim 1, wherein: the molar ratio of the chiral rhodium catalyst to the 1-phenylpropane-1-en-1-yl acetate compound in the reaction medium is 1:10 to 100.
5. The method for synthesizing the chiral 1-phenylpropyl acetate compound according to claim 1, wherein:
under the protection of nitrogen, the chiral rhodium catalyst is prepared by reacting a rhodium salt catalyst precursor and a chiral ferrocenyl phosphine-phosphoramidite ligand in situ according to the molar ratio of 1.0: 0.5-5.0, stirring in a reaction medium for 0.5-2 hours to prepare the chiral rhodium catalyst.
6. The method for synthesizing the chiral 1-phenylpropyl acetate compound according to claim 5, wherein: the rhodium salt catalyst precursor is [ Rh (COD) ]2]BF4、[Rh(CO)2(acac)]、[Rh(COD)Cl]2、[Rh(COD)2]OTf、[Rh(C2H4)2Cl]2、[Rh(OAc)2]。
7. The method for synthesizing chiral phenylpropyl 1-acetate according to claim 5, wherein:
the chiral ferrocenylphosphine-phosphoramidite ligand has the following IV or V structure:
Figure FDA0002756270040000021
in the formula (S)c,Rp,Sa) -IV and (R)c,Sp,Ra) -V are enantiomers of each other;
in the formula: ar is phenyl and substituted phenyl, naphthyl and substituted naphthyl, and contains one or more than two five-membered or six-membered heterocyclic aromatic groups of oxygen, sulfur and nitrogen atoms; the substituent on the substituted phenyl or the substituted naphthyl is one or more than two of C1-C40 alkyl, C1-C40 alkoxy, halogen, nitro, ester group or cyano, and the number of the substituent is 1-5; r4、R5Is one or two of C1-C40 alkyl, C3-C12 cycloalkyl, phenyl and substituted phenyl, five-membered or six-membered heterocyclic aromatic group containing one or more than two oxygen, sulfur and nitrogen atoms, benzyl and substituted benzyl, naphthyl and substituted naphthyl; the substituents on the phenyl, benzyl and naphthyl are one or two of C1-C40 alkyl, C1-C40 alkoxy, halogen, nitro, ester group or cyanoThe above.
8. The method for synthesizing the chiral 1-phenylpropyl acetate compound according to claim 5, wherein: the molar ratio of the rhodium salt catalyst precursor, the chiral ferrocenylphosphine-phosphoramidite ligand and the 1-phenylpropan-1-en-1-yl acetate compound in the reaction medium is 1.0: 0.5-5.0: 10-100.
9. The method for synthesizing the chiral 1-phenylpropyl acetate compound according to claim 1, wherein:
the reaction medium is one or more of protic solvent or aprotic solvent, and is one or more of methanol, ethanol, isopropanol, n-propanol, tert-butanol, trifluoroethanol, acetic acid or dichloromethane, 1, 2-dichloroethane, tetrahydrofuran, benzene, and toluene.
10. The method for synthesizing the chiral 1-phenylpropyl acetate compound according to claim 1, wherein:
the catalytic reaction conditions are as follows:
temperature: -40 ℃ to 50 ℃;
pressure: p (H)2)＝1-100bar；
Time: 0.5-24 hours.
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