CN116041393B - N-N axis chiral bisindolyl phosphine ligand and synthetic method and application thereof - Google Patents
N-N axis chiral bisindolyl phosphine ligand and synthetic method and application thereof Download PDFInfo
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
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Abstract
An N-N axis chiral bisindolyl phosphine ligand, a synthesis method and application thereof, wherein the chemical structural formula is shown in formula 4; the preparation method comprises the following steps: using indole derivative enamine and 2, 3-diketone ester as raw materials, using
Molecular sieve is used as dehydrating agent, hexafluoroisopropanol is used as additive, 1, 2-tetrachloroethane is used as reaction solvent, stirring reaction is carried out under the catalysis of chiral phosphoramide at 70 ℃, TLC tracking reaction is carried out until the compound N-N axis chiral bisindole derivative of formula 3 is obtained; the compound of formula 4 is obtained by taking N-N axis chiral bisindole derivative of the compound of formula 3, trichlorosilane and triethylamine as raw materials, adding toluene, stirring and reacting at 120 ℃, and carrying out TLC tracking reaction until the reaction is finished. The ligand prepared by the invention has excellent stereoselectivity control effect on asymmetric reaction catalyzed by metal, and can be applied to asymmetric allylation reaction catalyzed by transition metal; the method has the advantages of mild reaction conditions, low cost and high enantioselectivity.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to an N-N axis chiral bisindolyl phosphine ligand, and a synthesis method and application thereof.
Background
The axichiral phosphine ligand is a chiral ligand with very wide application and plays an important role in asymmetric reactions catalyzed by transition metals. However, currently, axichiral phosphine ligands are concentrated in phosphine ligands derived from an axichiral binaphthyl skeleton. The N-axis chiral bisindole phosphine ligand has no literature report at present, and the N-axis chiral bisindole phosphine ligand can provide a wider dihedral angle regulation space, more hydrogen bond activation sites and more electric adjustment space compared with a binaphthyl derivative phosphine ligand, so that the N-axis chiral bisindole phosphine ligand is expected to have better enantioselectivity control capability compared with the existing axial chiral binaphthyl derivative phosphine ligand.
Disclosure of Invention
It is an object of the present invention to provide an N-axis chiral bisindole phosphine ligand having an excellent stereoselective control effect.
The second purpose of the invention is to provide a synthesis method of the N-N axis chiral bisindole phosphine ligand, which has the advantages of mild reaction conditions, low cost and high enantioselectivity.
The invention also provides an application of the N-axis chiral bisindole phosphine ligand, and the catalyst can be applied to asymmetric allylation reaction catalyzed by transition metal.
In order to achieve the above purpose, the invention adopts the following technical scheme: an N-N axis chiral bisindolyl phosphine ligand has a chemical structural formula shown in a formula 4:
the invention also provides a synthesis method of the N-axis chiral bisindolyl phosphine ligand, which comprises the following steps:
(1) Using indole derivative enamine of formula 1 and 2, 3-diketone ester of formula 2 as reaction raw materials to obtain the final product
Molecular sieve is dehydrating agent, hexafluoroisopropanol is additive, 1, 2-tetrachloroethane is used as reaction solvent, stirring reaction is carried out under the catalysis of chiral phosphoramide catalyst and 70 ℃, TLC tracking reaction is carried out until completion, and filtering, concentrating, purifying and recrystallizing are carried out to obtain the N-N axis chiral bisindole derivative of the compound of formula 3;
wherein, the mol ratio of the compound of formula 1, the indole derivative enamine, the compound of formula 2, 3-diketone ester, the chiral phosphoramide catalyst and hexafluoroisopropanol is 1:2:0.1:2; the compound of formula 1, indole-derived enamine, to 1, 2-tetrachloroethane, was used in an amount ratio of 1mmol:5mL; indole-derived enamines of the formula 1
The molecular sieve dosage ratio is 1mmol:1g;
the structural formula of the indole derivative enamine of the compound of the formula 1 is
The structural formula of the 2, 3-diketone ester of the compound of the formula 2 is
The structural formula of the N-axis chiral bisindole derivative of the compound of the formula 3 is
(2) Adding toluene into the raw materials of trichlorosilane, triethylamine and the N-axis chiral bisindole derivative of the compound shown in the formula 3 prepared in the step (2), stirring the mixture at 120 ℃ for reaction, quenching the mixture by using saturated sodium bicarbonate solution after TLC tracking reaction is finished, extracting the mixture by using ethyl acetate, concentrating the mixture, and purifying the mixture to obtain a compound shown in the formula 4;
wherein, the molar ratio of the N-N axis chiral bisindole derivative, the trichlorosilane and the triethylamine of the compound shown in the formula 3 is 1:10:25, a step of selecting a specific type of material; the dosage ratio of the N-axis chiral bisindole derivative of the compound of formula 3 to toluene is 1mmol:10mL;
the structural formula of the compound of the formula 4 is
Preferably, the chiral phosphoramide catalyst is a compound of formula 5, and the structural formula of the compound of formula 5 is
Preferably, the purification in the step (1) is silica gel column chromatography, and the volume ratio of eluent is 4:1 petroleum ether/ethyl acetate mixture.
Preferably, the purification in the step (2) is silica gel column chromatography, and the volume ratio of eluent is 10:1 petroleum ether/ethyl acetate mixture.
The invention also provides application of the N-axis chiral bisindolylphosphine ligand in asymmetric allylation reaction catalyzed by transition metal, wherein the asymmetric allylation reaction has the reaction formula:
compared with the prior art, the invention has the following beneficial effects:
(1) The N-N axis chiral bisindolyl phosphine ligand synthesized by the method can be applied to asymmetric allylation reaction catalyzed by transition metal;
(2) In the invention, chiral phosphoramide is used as a catalyst in the process of synthesizing the N-N axis chiral bisindole phosphine ligand, so that extremely high enantioselectivity is obtained; the reaction condition is more conventional, the reaction process is mild, simple and convenient, the operation is easy, the cost is low, and the method is suitable for industrialized mass production.
Detailed Description
The present invention will be described in further detail with reference to examples.
In the examples below, unless otherwise indicated, indole-derived enamines, 2, 3-diketones, chiral phosphoramide catalysts and other reagents are commercially available or available in a manner reported in the known literature; the experimental methods are generally carried out under conventional conditions or conditions recommended by the manufacturer.
Example 1
The synthetic route of the N-axis chiral bisindole derivative of the compound of formula 3 is as follows:
0.1mmol of indole-derived enamine formula 1 and 0.2mmol of 2, 3-diketone ester derivative formula 2 are added as reactants in a solvent under the action of 0.01mol (10 mol% of indole-derived enamine) of chiral phosphoramide formula 5 at 100mg
Molecular sieve, 0Stirring and reacting for 12h at 70 ℃ in the presence of 2mmol hexafluoroisopropanol, performing TLC tracking reaction till the completion, filtering, concentrating, and purifying and separating by silica gel column chromatography (eluent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 4:1), thereby obtaining the N-axis chiral bisindole derivative of the compound shown in the formula 3, wherein the yield, the stereoselectivity and the structural characterization data are as follows: 53% yield (35.7 mg) as a yellow solid.m.p.180.0-180.5 ℃; [ alpha ]] D 20 ＝-7.5(c 0.55,Acetone)； 1 H NMR(400MHz,CDCl 3 )δ11.23(s,1H),7.97–7.39(m,2H),7.35–7.30(m,3H),7.29–7.27(m,3H),7.26–7.22(m,3H),7.21–7.10(m,4H),7.10–7.03(m,4H),7.02–6.96(m,2H),6.96–6.89(m,3H),6.84–6.78(m,1H),6.64(d,J＝7.9Hz,1H),5.89(d,J＝8.1Hz,1H),4.22–4.04(m,2H),0.91(t,J＝7.1Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ168.2,151.6,146.8,139.9,139.8,138.3,132.7,132.0,131.8,131.7,131.6,131.5,131.4,130.5,130.3,129.6,129.5,129.2,129.0,127.9,127.8,127.7,126.9,126.7,126.2,126.1,125.7,122.5,121.3,113.1,109.8,108.7,105.4,100.4,61.2,13.5； 31 PNMR(162MHz,CDCl 3 )δ17.0；IR(KBr):3869,3750,3675,1761,1576,1436,1395,1276,1154,1067,795,698cm -1 ；ESI FTMS exactmass calcd for(C 43 H 33 N 2 O 4 P+Na) + requires m/z 695.2070,found m/z 695.2060；The enantiomeric excess:82％,determined by HPLC(IE,hexane/isopropanol＝70/30,flow rate 1.0mL/min,I＝254nm)t R ＝19.877min(major),t R ＝24.337min(minor).
Example 2
The synthetic route of the N-axis chiral bisindolylphosphine ligand of the compound of formula 4 is as follows:
0.1mmol of the compound of formula 3 (recrystallised to 99% ee) is dissolved in 1mL of toluene, 1mmol of trichlorosilane and 2.5mmol of triethylamine are added, the mixture is reacted at 120 ℃ for 6 hours, after the reaction is finished, the mixture is quenched with saturated sodium bicarbonate solution, extracted with ethyl acetate, concentrated and then passed throughPurifying and separating by silica gel column chromatography (eluting solution is mixed solution of petroleum ether and ethyl acetate with volume ratio of 10:1) to obtain N-N axis chiral bisindolylphosphine ligand of formula 4, and the data of yield, stereoselectivity and structural characterization are as follows: 83% yield (54.7 mg) as awhite solid.m.p.137.6-139.1 ℃; [ alpha ]] D 20 ＝-84.0(c0.21,Acetone)； 1 H NMR(400MHz,CDCl 3 )δ11.32(s,1H),7.43–7.25(m,6H),7.22–7.13(m,2H),7.13–7.04(m,5H),7.04–6.86(m,9H),6.83–6.79(m,2H),6.78–6.74(m,2H),5.96(d,J＝8.1Hz,1H),4.27–4.05(m,2H),0.93(t,J＝7.1Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ168.3,151.7,146.7,139.6,139.5,138.9,133.4,133.3,133.2,133.0,132.9,132.8,132.3,132.1,130.5,129.3,129.1,128.5,128.0,127.9,127.8,127.7,127.5,127.4,126.6,126.2,125.2,122.0,120.7,113.2,109.6,109.2,105.1,100.9,61.4,13.5； 31 P NMR(162MHz,CDCl 3 )δ-27.5；IR(KBr):3443,3028,1758,1639,1453,1317,1259,1157,966,800,697cm -1 ；ESI FTMS exact mass calcd for(C 43 H 33 N 2 O 3 P+H) + requires m/z 657.2302,foundm/z 657.2282；The enantiomeric excess:99％,determined by HPLC(IC,hexane/isopropanol＝95/5,flow rate 1.0mL/min,I＝254nm)t R ＝8.406min(minor),t R ＝12.369min(major).
Example 3
The synthetic route of the N-axis chiral bisindolylphosphine ligand applied to the asymmetric allylation reaction catalyzed by transition metal is as follows:
0.1mmol of allyl acetate of the compound of formula 6, 0.005mmol (5 mol% of the compound of formula 6) of [ Pd (C) 3 H 5 )Cl] 2 0.01mmol (10 mol% of the compound of formula 6) of the N-N axis chiral bisindolephosphine ligand of the compound of formula 4 is dissolved in 1mL of dichloromethane and stirred at room temperature for 30 minutes; then cooling to 0deg.C, sequentially adding 0.3mmol N, O-bis (trimethylsilyl) acetamide (BAS), 0.04mmol potassium acetate, and 0.3mmol compound of formula 7And (3) continuing to react at the temperature of 0 ℃ for the dimethyl malonate, carrying out TLC (thin-layer chromatography) tracking reaction until the reaction is finished, filtering, concentrating, and purifying and separating by a silica gel column (eluent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 20:1), thereby obtaining the N-axis chiral bisindole compound shown in the formula 8, wherein the data of yield, stereoselectivity and structural characterization are as follows:
95％yield(30.8mg)as a colorless oil.[α] D 20 ＝24.7(c 0.35,Acetone)； 1 HNMR(400MHz,CDCl 3 )δ7.43–7.26(m,8H),7.26–7.17(m,2H),6.49(d,J＝15.8Hz,1H),6.38–6.30(m,1H),4.35–4.22(m,1H),3.97(d,J＝10.9Hz,1H),3.71(s,3H),3.53(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ168.2,167.8,140.2,136.8,131.8,129.1,128.7,128.5,127.9,127.6,127.2,126.4,57.7,52.7,52.6,49.2；IR(KBr):3443,3033,1653,1626,1484,1256,1177,1043,766,744,695cm -1 ；ESI FTMS exact mass calcd for(C 20 H 20 O 4 +Na) + requires m/z347.1254,foundm/z 347.1240；The enantiomeric excess:90％,determinedbyHPLC(IA,hexane/isopropanol＝80/20,flowrate 0.8mL/min,I＝254nm)t R ＝7.446min(major),t R ＝8.883min(minor).
from example 3, it can be seen that the N-axis chiral bisindolylphosphine ligand of formula 4 has excellent stereoselective control in transition metal catalyzed asymmetric allylation reactions.
Claims (5)
1. The N-N axis chiral bisindolyl phosphine ligand is characterized in that the chemical structural formula is shown as formula 4:
2. a method of synthesizing the N-N axis chiral bisindolylphosphine ligand of claim 1, comprising the steps of:
(1) The indole derivative enamine of the formula 1 and the 2, 3-diketone ester of the formula 2 are used as reaction raw materials,to be used for
Molecular sieve is dehydrating agent, hexafluoroisopropanol is additive, 1, 2-tetrachloroethane is used as reaction solvent, stirring reaction is carried out under the catalysis of chiral phosphoramide catalyst formula 5 and 70 ℃, TLC tracking reaction is carried out until completion, and filtering, concentrating, purifying and recrystallizing are carried out to obtain the N-N axis chiral bisindole derivative of the compound of formula 3;
wherein, the mol ratio of the compound of formula 1, the indole derivative enamine, the compound of formula 2, 3-diketone ester, the chiral phosphoramide catalyst and hexafluoroisopropanol is 1:2:0.1:2; the compound of formula 1, indole-derived enamine, to 1, 2-tetrachloroethane, was used in an amount ratio of 1mmol:5mL; indole-derived enamines of the formula 1
The molecular sieve dosage ratio is 1mmol:1g;
the structural formula of the indole derivative enamine of the compound of the formula 1 is
The structural formula of the 2, 3-diketone ester of the compound of the formula 2 is
The structural formula of the N-axis chiral bisindole derivative of the compound of the formula 3 is
The structural formula of the compound of the formula 5 is
(2) Adding toluene into the raw materials of trichlorosilane, triethylamine and the N-axis chiral bisindole derivative of the compound shown in the formula 3 prepared in the step (2), stirring the mixture at 120 ℃ for reaction, quenching the mixture by using saturated sodium bicarbonate solution after TLC tracking reaction is finished, extracting the mixture by using ethyl acetate, concentrating the mixture, and purifying the mixture to obtain a compound shown in the formula 4;
wherein, the molar ratio of the N-N axis chiral bisindole derivative, the trichlorosilane and the triethylamine of the compound shown in the formula 3 is 1:10:25, a step of selecting a specific type of material; the dosage ratio of the N-axis chiral bisindole derivative of the compound of formula 3 to toluene is 1mmol:10mL;
the structural formula of the compound of the formula 4 is
3. The method for synthesizing the N-axis chiral bisindolylphosphine ligand according to claim 2, wherein the purification in the step (1) is silica gel column chromatography, and the volume ratio of the eluent is 4:1 petroleum ether/ethyl acetate mixture.
4. The method for synthesizing the N-axis chiral bisindolylphosphine ligand according to claim 2, wherein the purification in the step (2) is silica gel column chromatography, and the volume ratio of the eluent is 10:1 petroleum ether/ethyl acetate mixture.
5. Use of an N-N axis chiral bisindolephosphine ligand as defined in claim 1 in a transition metal catalyzed asymmetric allylation reaction of the formula:
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