Chiral pyrroloimidazolone-xanthene-triphenylphosphine ligand pi-xan-phos, its preparation method and application in asymmetric catalytic reaction

Abstract

The application discloses a chiral pyrroloimidazolone-xanthene-triphenylphosphine ligand. The application generates a target product chiral pyrroloimidazolone-xanthene-triphenylphosphine ligand through condensation reaction of corresponding prolyl arylamine 1 and triphenylphosphine xanthene formaldehyde 2. The ligand comprises a triphenylphosphine group, a xanthene group and a chiral pyrroloimidazolone group. The chiral pyrroloimidazolone group can provide a chiral cavity environment, the xanthene group can provide a rigid skeleton, and the phosphorus atom of the triphenylphosphine group belongs to an electron-rich coordination site, can form coordination with metal, thereby generating a chiral ligand metal phosphine complex, and the application in catalyzing asymmetric allyl alkylation of alcohol. Therefore, the ligand has important application value in the field of asymmetric catalytic synthesis, and the synthesis method is very economical and simple. The ligand also has good air stability, wide applicability and good compatibility for various substituents.

Description

Technical Field

[0001] This invention relates to the fields of chiral chemistry and asymmetric catalytic synthesis, and in particular to a chiral pyrrolidinidone-oxanthracene-triphenylphosphine ligand PI-Xan-Phos, its preparation method, and its application in catalytic asymmetric allyl alkylation reactions. Background Technology

[0002] Chiral pharmaceuticals are a cutting-edge field in the pharmaceutical industry. The Nobel Prizes in Chemistry in 2001 and 2021 were awarded to major contributors to chiral catalysis. Currently, there are approximately 2,000 drugs in use worldwide, with chiral drugs accounting for more than 50%. Among the 250 commonly used drugs in clinical practice, as many as 200 are chiral.

[0003] Key technologies for the preparation of chiral drugs have been selected as one of the "Top Ten Chemical Inventions That Changed the World" by IUPAC. Asymmetric catalysis has become a crucial tool for the enantioselective synthesis of drugs, natural products, and fine chemicals. One of the core scientific problems in asymmetric catalysis technology is the creation of dominant chiral ligands and catalysts. The design and synthesis of original dominant chiral ligands play a key role in the development of asymmetric catalytic reactions and are the most attractive and challenging goals in asymmetric catalysis, providing core technologies for the efficient and green synthesis of chiral drugs and drug candidates. Furthermore, economically feasible synthetic routes are also essential for dominant chiral ligands, enabling their widespread application. In particular, the phosphine atom of triphenylphosphine belongs to an electron-rich coordination site, and the unique nature of the lone pair electrons of the phosphine atom provides opportunities to form complexes with various metals. Some research focuses on developing novel chiral triphenylphosphine ligands for metal-catalyzed reactions.

[0004] Against this backdrop, we designed and developed a novel type of chiral pyrrolidinidone-oxanthracene-triphenylphosphine ligand, PI-Xan-Phos, and tested their application in catalytic asymmetric allyl alkylation reactions. Summary of the Invention

[0005] The purpose of this invention is to provide a chiral pyrrolizimidazolone-oxanthracene-triphenylphosphine ligand PI-Xan-Phos, its preparation method, and its applications. This is an important class of chiral triphenylphosphine ligands, comprising a triphenylphosphine group, an oxanthracene group, and a chiral pyrrolizimidazolone group. The chiral pyrrolizimidazolone group provides a chiral cavity environment, the oxanthracene group provides a rigid framework, and the phosphine atom in the triphenylphosphine group is an electron-rich coordination site that can coordinate with a metal, thereby generating a chiral ligand-metal phosphine complex. This complex is used as a chiral ligand in asymmetric catalytic reactions. Therefore, this type of ligand has significant application value in the field of asymmetric catalytic synthesis, and its synthesis method is very economical and simple. It also exhibits good air stability, wide applicability, and good compatibility with various substituents.

[0006] The present invention is achieved as follows: a chiral pyrrolipidazolone-oxanthracene-triphenylphosphine ligand PI-Xan-Phos, the compound having a structure as shown in general formula (I);

[0007] (I);

[0008] In the formula, R 1 It can be hydrogen / methyl / halogen or methoxy; R 2 It can be hydrogen or hydroxyl.

[0009] Specifically, it is one of the following structural formulas:

[0010] .

[0011] A method for preparing the chiral pyrroloimidazole-oxanthracene-triphenylphosphine ligand PI-Xan-Phos involves a condensation reaction of the corresponding prolyl arylamine 1 with triphenylphosphine-type oxanthracene formaldehyde 2 to generate the target product, the chiral pyrroloimidazole-oxanthracene-triphenylphosphine ligand PI-Xan-Phos.

[0012] The synthesis route is as follows:

[0013] ;

[0014] The present invention also discovers the application of chiral pyrrolipidazolone-oxanthracene-triphenylphosphine (PI-Xan-Phos) as a ligand in the catalytic asymmetric allyl alkylation reaction.

[0015] By employing the above-mentioned technical solution, the corresponding prolyl arylamine 1 undergoes a condensation reaction with triphenylphosphine-based oxanthracene formaldehyde 2 to generate the target product, the chiral pyrroloimidazolone-oxanthracene-triphenylphosphine ligand PI-Xan-Phos. This type of ligand comprises a triphenylphosphine group, an oxanthracene group, and a chiral pyrroloimidazolone group. The chiral pyrroloimidazolone group provides a chiral cavity environment, the oxanthracene group provides a rigid framework, and the phosphine atom of the triphenylphosphine group is an electron-rich coordination site that can coordinate with a metal, thereby generating a chiral ligand-metal phosphine complex, which can be used as a chiral ligand in asymmetric catalytic reactions. Therefore, this type of ligand has significant application value in the field of asymmetric catalytic synthesis, and its synthetic method is very economical and simple. It also exhibits good air stability, wide applicability, and good compatibility with various substituents. Attached Figure Description

[0016] Figure 1 The design concept and inventive diagram of the chiral pyrroloimidazole one-oxanthracene-triphenylphosphine ligand PI-Xan-Phos synthesized in this invention;

[0017] Figure 2 This is a single crystal image of the chiral ligand PI-Xan-Phos-1 synthesized in this invention;

[0018] Figure 3 and Figure 4 The spectral data of the chiral ligand PI-Xan-Phos-1 in this embodiment of the invention are shown. Detailed Implementation

[0019] (I) Preparation of chiral pyrrolipidone-oxanthracene-triphenylphosphine PI-Xan-Phos

[0020]

[0021] Preparation of chiral pyrrolipid-oxanthracene-triphenylphosphine PI-Xan-Phos: Prolyl arylamine raw material 1 (1.5 eq, 1.5 mmol) and triphenylphosphine-based oxanthracene formaldehyde 2 (1 eq, 1.0 mmol) were dissolved in 15 mL of anhydrous ethanol and refluxed in an oil bath at 85 °C for 12 h. After post-treatment, the reaction solution was purified by column chromatography to obtain a white solid PI-Xan-Phos-1 with a melting point of 211.7–212.5 °C. o C, [α] D 20 = +52.3 (c 0.10, EtOH); Yield 75%, >20:1dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1H NMR (CDCl3, 600 MHz) δ: 1.55 (s,3H), 1.58 (s, 3H), 1.74-1.80 (m, 2H), 2.07-2.13 (m, 2H), 2.76-2.80 (m, 1H),3.57-3.60 (m, 1H), 3.93-3.96 (m, 1H), 6.08 (s, 1H), 6.46-6.48 (m, 1H), 6.84-6.88 (m, 2H), 6.90-6.95 (m, 2H), 7.01-7.04 (m, 2H), 7.08 (d, J = 7.8 Hz, 2H),7.19-7.24 (m, 6H), 7.27-7.31 (m, 5H), 7.37 (d, J = 7.8 Hz, 1H); 13 C NMR(CDCl3, 150 MHz) δ: 24.8, 27.4, 31.9, 33.3, 34.3, 55.9, 64.5, 76.6, 120.7,123.3 (d, J CP = 57.2 Hz), 124.5, 124.6 (d, J CP = 13.5 Hz), 126.3 (d, J CP = 21.0Hz), 127.2, 128.6 (d, J CP = 7.5 Hz), 128.7, 128.8, 128.9 (d, J CP = 6.2 Hz),129.2, 129.6, 130.5, 131.8, 133.7 (d, J CP = 19.5 Hz), 134.1 (d, J CP = 19.5Hz), 136.3 ((d, J CP = 36.1 Hz), 137.4, 147.7, 151.6 (d, J CP = 13.5 Hz), 175.4; 31 P NMR (CDCl3, 162 MHz) δ: -16.7; HRMS (ESI-TOF) m / z: Calcd. for C 39 H 36 N2O2P [M+H] + : 595.2509; Found: 595.2501。

[0022] The chiral ligands PI-Xan-Phos-2 to PI-Xan-Phos-20 prepared by the examples were prepared using the same method as chiral ligand PI-Xan-Phos-1, with the same feed ratio, to obtain chiral ligands PI-Xan-Phos-2 to PI-Xan-Phos-20. The reaction yields are shown in Table 1. However, it should be emphasized that the examples are intended to illustrate, not limit, the scope of the invention. The compounds of the present invention are not limited to those shown in Table 1.

[0023] Table 1 shows the chemical structures of the prepared chiral pyrrolipid-imidazolone-oxanthracene-triphenylphosphine (PI-Xan-Phos).

[0024]

[0025] PI-Xan-Phos-2: White solid, melting point: 97.6-98.9°C. o C, [α] D 20 = +46.2 (c 0.10, EtOH); Yield 67%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1 H NMR (CDCl3, 600 MHz) δ: 1.63 (s, 3H), 1.65 (s, 3H), 1.82-1.86 (m, 2H), 2.13-2.18 (m, 2H), 2.22 (s, 3H), 2.82-2.86 (m, 1H), 3.61-3.64 (m, 1H), 4.00-4.02 (m, 1H), 6.14(s, 1H), 6.53-6.55 (m, 1H), 6.90-6.96 (m, 4H), 7.00-7.05 (m, 3H), 7.27-7.38(m, 11H), 7.44 (d, J = 7.8 Hz, 1H); 13 C NMR (CDCl3, 150 MHz) δ: 20.9, 24.8,27.3, 31.8, 33.3, 34.2, 55.9, 64.5, 76.6, 120.8, 123.3, 123.7 (d, J CP = 9.0Hz), 124.5 (d, J CP = 15.1 Hz), 126.2, 126.5, 127.2, 128.6 (d, J CP= 6.1 Hz), 128.8, 128.9 (d, J CP = 3.2 Hz), 129.1, 129.3, 129.6, 130.5, 131.7, 133.6 (d,J CP = 19.5 Hz), 134.1, 134.2 (d, J CP = 19.5 Hz), 134.8, 136.3 (d, J CP = 18.3Hz), 147.7, 151.6, 175.2; 31 P NMR (CDCl3, 162 MHz) δ: -16.7; HRMS (ESI-TOF) m / z: Calcd. for C 40 H 38 N2O2P [M+H] + : 609.2665; Found: 609.2657.

[0026] PI-Xan-Phos-3: White solid, melting point: 101.3-101.9 ppm. o C, [α] D 20 = +77.8 (c 0.10, EtOH); Yield 68%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1 H NMR (CDCl3, 600 MHz) δ: 1.62 (s, 3H), 1.64 (s, 3H), 1.80-1.85 (m, 2H), 2.13-2.19 (m, 2H), 2.21 (s, 3H), 2.78-2.82 (m, 1H), 3.53-3.56 (m, 1H), 4.01-4.03 (m, 1H), 6.18(s, 1H), 6.55-6.57 (m, 1H), 6.69 (d, J = 8.4 Hz, 1H), 6.81 (d, J = 7.2 Hz, 1H), 6.93-6.96 (m, 3H), 6.99-7.02 (m, 1H), 7.27-7.38 (m, 11H), 7.43 (d, J =7.8 Hz, 1H), 7.46 (s, 1H); 13C NMR (CDCl3, 150 MHz) δ: 21.6, 24.8, 27.5, 31.7,33.1, 34.3, 55.8, 64.6, 77.3, 117.8, 121.5, 123.4, 123.7 (d, J CP = 7.5 Hz), 124.6 (d, J CP = 15.3 Hz), 125.5, 126.2, 126.6, 127.1, 128.6, 128.7 (d, J CP =7.5 Hz), 128.7, 128.8 (d, J CP = 12.0 Hz), 129.2, 129.8, 130.7, 131.8, 133.8,133.9, 134.1, 136.3 (d, J CP = 25.5 Hz), 137.4, 138.5, 147.8, 151.8 (d, J CP =16.5 Hz), 175.3; 31 P NMR (CDCl3, 162 MHz) δ: -16.8; HRMS (ESI-TOF) m / z: Calcd.for C 40 H 38 N2O2P [M+H] + : 609.2665; Found: 609.2643.

[0027] PI-Xan-Phos-4: White solid, melting point: 86.4-86.9°C. o C, [α] D 20 = +75.3 (c 0.10, EtOH); Yield 66%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1H NMR (CDCl3,600 MHz) δ: 1.41 (s, 3H), 1.63 (s, 3H), 1.76-1.80 (m, 1H), 1.85-1.90 (m, 1H),2.16-2.18 (m, 2H), 2.20 (s, 3H), 2.77-2.81 (m, 1H), 3.06-3.10 (m, 1H), 4.16-4.18 (m, 1H), 6.12 (s, 1H), 6.49-6.51 (m, 1H), 6.69 (d, J = 7.8 Hz, 1H),6.80-6.83 (m, 1H), 6.94-6.96 (m, 1H), 7.00-7.02 (m, 1H), 7.07 (d, J = 7.8 Hz,1H), 7.10-7.13 (m, 1H), 7.24-7.32 (m, 11H), 7.37 (d, J = 7.8 Hz, 1H), 7.43(d, J = 7.2 Hz, 1H); 13 C NMR (CDCl3, 150 MHz) δ: 18.8, 25.1, 28.7, 30.8, 31.9,34.5, 55.9, 64.7, 78.1, 123.4, 123.7, 124.3 (d, J CP = 15.2 Hz), 125.5, 125.7,126.2, 126.7, 127.4 (d, J CP = 1.5 Hz), 127.5, 127.7, 128.6 (d, J CP = 3.0 Hz),128.7 (d, J CP = 1.5 Hz), 128.7, 128.9, 130.3, 130.9, 131.0, 131.9, 133.6 (d,J CP = 19.5 Hz), 133.9 (d, J CP = 21.0 Hz), 134.5, 136.0, 136.6 (d, J CP = 24.2Hz), 148.4, 152.4 (d, J CP = 16.5 Hz), 173.9; 31 P NMR (CDCl3, 162 MHz) δ: -17.2;HRMS (ESI-TOF) m / z: Calcd. for C40 H 38 N2O2P [M+H] + : 609.2665; Found: 609.2688.

[0028] PI-Xan-Phos-5: White solid, melting point: 108.1-108.5 °C. o C, [α] D 20 = +53.2 (c 0.10, EtOH); Yield 68%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1 H NMR (CDCl3, 600 MHz) δ: 1.62 (s, 3H), 1.63 (s, 3H), 1.82-1.87 (m, 2H), 2.14-2.18 (m, 2H), 2.85-2.89 (m, 1H), 3.59-3.62 (m, 1H), 3.71 (s, 3H), 4.02-4.04 (m, 1H), 6.13 (s, 1H), 6.53-6.55 (m, 1H), 6.62 (d, J = 9.0 Hz, 2H), 6.96-6.97 (m, 2H), 6.99-7.05 (m, 3H), 7.26-7.38 (m, 11H), 7.43 (d, J = 7.8 Hz, 1H); 13 C NMR (CDCl3, 150 MHz) δ: 24.9, 27.5, 31.9, 33.1, 34.3, 55.3, 56.0, 64.5, 76.9,114.0, 122.7, 123.3, 123.7 (d, J CP = 25.5 Hz), 124.5 (d, J CP = 15.1 Hz),126.2, 126.6, 127.1, 128.6 (d, J CP = 7.5 Hz), 128.8 (d, J CP = 6.3 Hz), 128.9,129.1, 129.7, 130.4 (d, J CP = 19.5 Hz), 131.8, 133.7 (d, J CP = 21.0 Hz), 134.1 (d, J CP= 19.5 Hz), 136.3 (d, J CP = 12.0 Hz), 147.8, 151.7 (d, J CP = 16.5 Hz), 156.4, 174.8; 31 P NMR (CDCl3, 162 MHz) δ: -16.7; HRMS (ESI-TOF) m / z: Calcd.for C 40 H 38 N2O3P [M+H] + : 625.2615; Found: 625.2612.

[0029] PI-Xan-Phos-6: White solid, melting point: 75.0-75.6°C. o C, [α] D 20 = +4.0 (c 0.10, EtOH); Yield 65%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1 H NMR (CDCl3, 600 MHz) δ: 1.45 (s, 3H), 1.55 (s, 3H), 1.68-1.73 (m, 1H), 1.82-1.86 (m, 1H), 2.08-2.15 (m, 2H), 2.83-2.87 (m, 1H), 3.11-3.15 (m, 1H), 4.05-4.08 (m, 1H),6.02 (s, 1H), 6.41-6.43 (m, 1H), 6.68-6.70 (m, 1H), 6.86-6.90 (m, 2H), 7.01-7.06 (m, 2H), 7.16-7.20 (m, 7H), 7.24-7.28 (m, 5H), 7.38 (d, J = 7.8 Hz, 1H),7.35-7.37 (m, 1H); 13 C NMR (CDCl3, 150 MHz) δ: 25.0, 28.3, 31.7, 31.8, 34.4, 56.0, 64.1, 78.0, 123.4, 123.7, 124.5 (d, J CP = 16.5 Hz), 125.3, 126.0, 126.7,127.1, 127.3, 128.5 (d, J CP= 7.5 Hz), 128.7 (d, J CP = 15.3 Hz), 129.2, 130.0,130.5, 130.8, 131.8, 132.8, 133.7, 133.8, 133.9, 136.7 (d, J CP = 30.0 Hz), 148.1, 152.1 (d, J CP = 16.5 Hz), 174.5; 31 P NMR (CDCl3, 162 MHz) δ: -17.3; HRMS(ESI-TOF) m / z: Calcd. for C 39 H 35 ClN2O2P [M+H] + : 629.2119; Found: 629.2112.

[0030] PI-Xan-Phos-8: White solid, melting point: 187.5-188.0°C. o C, [α] D 20 = +91.4 (c 0.10, EtOH); Yield 66%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1 H NMR (CDCl3, 600 MHz) δ: 1.63 (s, 3H), 1.68 (s, 3H), 1.82-1.85 (m, 2H), 2.15-2.18 (m, 2H), 2.76-2.81 (m, 1H), 3.60-3.61 (m, 1H), 4.00-4.02 (m, 1H), 6.08 (s, 1H), 6.55-6.56 (m, 1H), 6.76-6.77 (m, 1H), 6.88 (d, J = 7.8 Hz, 1H), 6.95-6.97 (m, 3H),7.01-7.03 (m, 1H), 7.24-7.38 (m, 11H), 7.45 (d, J = 7.8 Hz, 1H), 7.66 (d, J =1.8 Hz, 1H); 13 C NMR (CDCl3, 150 MHz) δ: 24.8, 27.4, 31.6, 33.2, 34.3, 55.8,64.5, 76.5, 118.3, 120.6, 123.5 (d, JCP = 10.5 Hz), 123.8, 124.6, 124.7,126.1, 126.4, 127.1, 128.6 (d, J CP = 7.5 Hz), 128.8 (d, J CP = 7.5 Hz), 128.9,129.3, 129.7, 129.8, 130.8, 131.7, 133.7 (d, J CP = 19.5 Hz), 134.1 (d, J CP =21.0 Hz), 134.4, 136.2 (d, J CP = 24.1 Hz), 138.6, 147.8, 151.6 (d, J CP = 15.2Hz), 175.6; 31 P NMR (CDCl3, 162 MHz) δ: -16.6; HRMS (ESI-TOF) m / z: Calcd. forC 39 H 35 ClN2O2P [M+H] + : 629.2119; Found: 629.2129.

[0031] PI-Xan-Phos-10: White solid, melting point: 96.3-96.7°C. o C, [α] D 20 = +6.6 (c 0.10, EtOH); Yield 64%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1H NMR (CDCl3,600 MHz) δ: 1.48 (s, 3H), 1.54 (s, 3H), 1.72-1.76 (m, 1H), 1.79-1.82 (m, 1H),2.06-2.13 (m, 2H), 2.81-2.85 (m, 1H), 3.36-3.40 (m, 1H), 4.00-4.02 (m, 1H),5.99 (s, 1H), 6.42-6.45 (m, 1H), 6.63-6.66 (m, 1H), 6.76-6.78 (m, 1H), 6.89-6.93 (m, 2H), 6.98-7.04 (m, 2H), 7.17-7.27 (m, 12H), 7.32 (d, J = 7.8 Hz,1H); 13 C NMR (CDCl3, 150 MHz) δ: 24.9, 27.6, 31.7, 32.5, 34.3, 55.9, 63.8,77.8, 116.6 (d, J CF = 19.5 Hz), 123.5 (d, J CP = 43.5 Hz), 124.0 (d, J CP = 12.0Hz), 124.2 (d, J CP = 3.0 Hz), 124.3 (d, J CP = 4.5 Hz), 124.5, 126.2, 126.9,127.0, 127.7, 128.5 (d, J CP = 7.5 Hz), 128.6 (d, J CP = 4.5 Hz), 128.7, 128.8,129.8, 130.6, 131.8, 133.7 (d, J CP = 19.5 Hz), 134.0 (d, J CP = 19.5 Hz), 136.5(d, J CP = 18.0 Hz), 148.0, 151.9 (d, J CP = 16.5 Hz), 157.8 (d, J CF = 252.4 Hz),174.8; 31 P NMR (CDCl3, 162 MHz) δ: -16.8; HRMS (ESI-TOF) m / z: Calcd. forC39 H 35 FN2O2P [M+H] + : 613.2415; Found: 613.2425.

[0032] PI-Xan-Phos-12: White solid, melting point: 201.3-202.8 °C. o C, [α] D 20 = +54.1 (c 0.10, EtOH); Yield 65%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1 H NMR (CDCl3, 600 MHz) δ: 1.63 (s, 3H), 1.68 (s, 3H), 1.83-1.87 (m, 2H), 2.15-2.19 (m, 2H), 2.79-2.83 (m, 1H), 3.68-3.70 (m, 1H), 3.99-4.01 (m, 1H), 6.06 (s, 1H), 6.54-6.56 (m, 1H), 6.67-6.70 (m, 1H), 6.80 (d, J = 8.4 Hz, 1H), 6.86 (d, J = 7.8Hz, 1H), 6.93-6.96 (m, 1H), 6.99-7.03 (m, 2H), 7.17-7.20 (m, 1H), 7.23-7.30(m, 5H), 7.32-7.38 (m, 6H), 7.44 (d, J = 7.8 Hz, 1H); 13 C NMR (CDCl3, 150 MHz)δ: 24.8, 27.3, 31.7, 33.4, 34.3, 55.8, 64.5, 76.6, 107.7 (d, J CF = 25.5 Hz), 111.1 (d, J CF = 21.0 Hz), 115.6, 123.4 (d, J CP = 9.0 Hz), 123.8, 124.7 (d, J CP = 13.5 Hz), 126.0, 126.5, 127.2, 128.7 (d, J CP = 6.0 Hz), 128.8 (d, J CP= 7.5Hz), 128.9, 129.3, 129.6, 129.9 (d, J CP = 9.1 Hz), 130.7, 131.7, 133.6 (d, J CP = 19.5 Hz), 134.2 (d, J CP = 19.5 Hz), 136.1 (d, J CP = 27.2 Hz), 139.9 (d, J CP =12.1 Hz), 147.7, 151.5 (d, J CF = 15.0 Hz), 162.6 (d, J CF = 243.3 Hz), 175.7; 31 P NMR (CDCl3, 162 MHz) δ: -16.6; HRMS (ESI-TOF) m / z: Calcd. for C 39 H 35 FN2O2P [M+H] + : 613.2415; Found: 613.2429.

[0033] PI-Xan-Phos-15: White solid, melting point: 98.9-99.6°C. o C, [α] D 20 = +101.9 (c 0.10, EtOH); Yield 72%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1 H NMR (CDCl3, 600 MHz) δ: 1.62 (s, 3H), 1.68 (s, 3H), 1.74-1.82 (m, 2H), 2.12-2.19 (m, 2H), 2.69-2.73 (m, 1H), 3.35-3.38 (m, 1H), 3.59 (s, 6H), 4.01-4.03 (m, 1H), 6.14-6.19 (m, 2H), 6.56-6.58 (m, 1H), 6.63 (d, J = 2.4 Hz, 2H), 6.93-7.03 (m, 3H),7.21-7.23 (m, 1H), 7.25-7.29 (m, 4H), 7.33-7.35 (m, 6H), 7.45 (d, J = 7.8 Hz,1H);13 C NMR (CDCl3, 150 MHz) δ: 24.8, 27.5, 31.3, 33.3, 34.4, 55.2, 55.7,64.7, 76.8, 97.4, 98.6, 123.6 (d, J CP = 4.5 Hz), 123.8, 124.7 (d, J CP = 15.2Hz), 126.2, 126.6, 127.1, 128.6 (d, J CP = 6.0 Hz), 128.7 (d, J CP = 7.5 Hz),129.2, 129.9, 130.9, 131.8, 133.7 (d, J CP = 48.0 Hz), 135.9 (d, J CP = 12.0Hz), 136.3 (d, J CP = 10.5 Hz), 139.2, 147.6, 151.9 (d, J CP = 16.5 Hz), 160.6, 175.6; 31 P NMR (CDCl3, 162 MHz) δ: -17.2; HRMS (ESI-TOF) m / z: Calcd. forC 41 H 40 N2O4P [M+H] + : 655.2720; Found: 655.2710.

[0034] PI-Xan-Phos-16: White solid, melting point: 124.5-125.7°C. o C, [α] D 20 = +74.9 (c 0.10, EtOH); Yield 70%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1H NMR (CDCl3,600 MHz) δ: 1.63 (s, 3H), 1.67 (s, 3H), 1.84-1.88 (m, 2H), 2.15-2.19 (m, 2H),2.82-2.86 (m, 1H), 3.65-3.68 (m, 1H), 4.00-4.02 (m, 1H), 6.10 (s, 1H), 6.54-6.56 (m, 1H), 6.85-6.87 (m, 1H), 6.94-6.96 (m, 1H), 7.01-7.04 (m, 3H), 7.18(d, J = 9.0 Hz, 2H), 7.26-7.37 (m, 11H), 7.45 (d, J = 7.8 Hz, 1H); 13 C NMR(CDCl3, 150 MHz) δ: 24.8, 27.4, 31.8, 33.2, 34.3, 55.9, 64.5, 76.4, 117.3,122.1, 123.4 (d, J CP = 18.2 Hz), 123.8, 124.5 (d, J CP = 15.1 Hz), 126.0,126.5, 127.2, 128.6 (d, J CP = 7.5 Hz), 128.8 (d, J CP = 7.5 Hz), 128.9, 129.3,129.6, 130.7, 131.7, 131.8, 133.6 (d, J CP = 19.5 Hz), 134.2 (d, J CP = 19.5Hz), 136.2 (d, J CP = 12.1 Hz), 136.5, 147.7, 151.5 (d, J CP = 16.5 Hz), 175.5; 31 P NMR (CDCl3, 162 MHz) δ: -16.7; HRMS (ESI-TOF) m / z: Calcd. for C 39 H 35 BrN2O2P [M+H] + : 673.1614; Found: 673.1608。

[0035] PI-Xan-Phos-17: White solid, melting point: 93.8-94.6°C. o C, [α] D 20 = +3.7 (c 0.10, EtOH); Yield 68%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1 H NMR (CDCl3, 600 MHz) δ: 1.53 (s, 3H), 1.54 (s, 3H), 1.75-1.79 (m, 2H), 2.06-2.10 (m, 2H), 2.76-2.81 (m, 1H), 3.54-3.58 (m, 1H), 3.93-3.95 (m, 1H), 6.03 (s, 1H), 6.45-6.47 (m, 1H), 6.66-6.69 (m, 2H), 6.82-6.84 (m, 1H), 6.85-6.88 (m, 1H), 6.91-6.93 (m, 1H), 6.99-7.01 (m, 2H), 7.17-7.29 (m, 10H), 7.34 (d, J = 7.8 Hz,1H); 13 C NMR (CDCl3, 150 MHz) δ: 24.9, 27.5, 31.9, 33.0, 34.3, 56.0, 64.5,76.9, 115.5 (d, J CF = 22.5 Hz), 122.6 (d, J CP = 7.5 Hz), 123.4, 123.8 (d, J CP =15.1 Hz), 124.5 (d, J CP = 15.2 Hz), 126.3, 126.4, 127.2, 128.7 (d, J CP = 6.1Hz), 128.8 (d, J CP = 6.2 Hz), 129.0, 129.2, 129.7, 130.7, 131.8, 133.4, 133.6(d, J CP = 19.5 Hz), 134.2 (d, J CP = 21.0 Hz), 136.3 (d, J CP = 19.5 Hz), 147.8, 151.6 (d, J CP= 16.5 Hz), 159.8 (d, J CF = 243.2 Hz), 175.2; 31 P NMR (CDCl3, 162MHz) δ: -16.7; HRMS (ESI-TOF) m / z: Calcd. for C 39 H 35 FN2O2P [M+H] + : 613.2415;Found: 613.2413.

[0036] PI-Xan-Phos-18: White solid, melting point: 126.4-127.1°C. o C, [α] D 20 = +20.5 (c 0.10, EtOH); Yield 70%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1 H NMR (CDCl3, 600 MHz) δ: 1.63 (s, 3H), 1.69 (s, 3H), 2.17-2.21 (m, 1H), 2.44-2.48 (m, 1H), 2.87-2.89 (m, 1H), 3.73-3.75 (m, 1H), 4.10-4.12 (m, 1H), 4.40 (s, 1H), 6.10(s, 1H), 6.54-6.56 (m, 1H), 6.89-6.91 (m, 1H), 6.94-6.97 (m, 1H), 6.99-7.04(m, 2H), 7.10-7.15 (m, 4H), 7.27-7.30 (m, 5H), 7.33-7.37 (m, 6H), 7.46 (d, J= 7.2 Hz, 1H); 13 C NMR (CDCl3, 150 MHz) δ: 31.4, 33.6, 34.3, 37.0, 62.5, 62.6,71.9, 75.9, 120.5, 123.2, 123.6 (d, J CP = 40.5 Hz), 124.4 (d, J CP = 15.2 Hz),124.6, 125.8, 126.4, 127.2, 128.7 (d, J CP = 7.5 Hz), 128.8 (d, JCP = 7.5 Hz), 128.9 (d, J CP = 4.5 Hz), 129.2, 129.6, 130.6, 131.8, 133.6 (d, J CP = 21.0 Hz), 134.2 (d, J CP = 19.5 Hz), 136.2 (d, J CP = 24.0 Hz), 137.3, 137.3, 147.9, 151.5(d, J CP = 16.5 Hz), 174.9; 31 P NMR (CDCl3, 162 MHz) δ: -16.5; HRMS (ESI-TOF) m / z: Calcd. for C 39 H 36 N2O3P [M+H] + : 611.2458; Found: 611.2458.

[0037] PI-Xan-Phos-19: White solid, melting point: 131.6-131.9°C. o C, [α] D 20 = +3.7 (c 0.10, EtOH); Yield 64%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1 H NMR (CDCl3, 600 MHz) δ: 1.56 (s, 3H), 1.63 (s, 3H), 2.17-2.21 (m, 1H), 2.38-2.42 (m, 1H), 3.03-3.05 (m, 1H), 3.29 (d, J = 10.8 Hz, 1H), 4.22-4.24 (m, 1H), 4.43 (s,1H), 5.99 (s, 1H), 6.47-6.49 (m, 1H), 6.77-6.79 (m, 1H), 6.95-6.99 (m, 2H),7.11-7.13 (m, 2H), 7.15-7.17 (m, 1H), 7.21-7.27 (m, 6H), 7.32-7.40 (m, 7H); 13C NMR (CDCl3, 150 MHz) δ: 31.6, 32.3, 34.4, 37.1, 62.1, 62.6, 71.9, 76.7,123.3, 123.8, 124.5, 124.6, 125.0, 126.2, 126.7 (d, J CP = 13.5 Hz), 127.2, 128.5 (d, J CP = 6.1 Hz), 128.7 (d, J CP = 7.5 Hz), 128.8 (d, J CP = 7.5 Hz),129.0, 129.9, 130.6, 130.9, 131.8, 132.7, 133.5, 133.7 (d, J CP = 13.5 Hz), 133.9 (d, J CP = 12.0 Hz), 136.3 (d, J CP = 10.5 Hz), 136.7 (d, J CP = 12.0 Hz), 148.1, 151.9 (d, J CP = 18.0 Hz), 148.1, 174.3; 31 P NMR (CDCl3, 162 MHz) δ: -16.9; HRMS (ESI-TOF) m / z: Calcd. for C 39 H 35 ClN2O3P [M+H] + : 645.2068; Found:645.2068.

[0038] PI-Xan-Phos-20: White solid, melting point: 146.3-147.2°C. o C, [α] D 20 = +16.7 (c 0.10, EtOH); Yield 65%, >20:1 dr; The results of nuclear magnetic resonance and high-resolution mass spectrometry tests are as follows: 1H NMR (CDCl3,600 MHz) δ: 1.64 (s, 3H), 1.71 (s, 3H), 2.06 (br s, 1H), 2.17-2.21 (m, 1H),2.42-2.46 (m, 1H), 2.81-2.83 (m, 1H), 3.67 (d, J = 10.2 Hz, 1H), 4.09-4.11(m, 1H), 4.39 (s, 1H), 6.01 (s, 1H), 6.54-6.56 (m, 1H), 6.71-6.72 (m, 1H),6.85 (d, J = 7.8 Hz, 1H), 6.95-6.99 (m, 3H), 7.02-7.05 (m, 1H), 7.23-7.37 (m,11H), 7.47 (d, J = 7.8 Hz, 1H), 7.65 (s, 1H); 13 C NMR (CDCl3, 150 MHz) δ:31.3, 33.5, 34.4, 37.0, 62.4, 62.6, 71.8, 75.9, 118.1, 120.4, 123.3 (d, J CP =10.5 Hz), 123.9, 124.4 (d, J CP = 15.1 Hz), 124.7, 125.4, 126.5, 127.1, 128.7(d, J CP = 7.5 Hz), 128.8 (d, J CP = 7.5 Hz), 128.9, 129.3, 129.7, 129.8, 130.9,131.8, 133.6 (d, J CP = 21.0 Hz), 134.1 (d, J CP = 21.1 Hz), 134.5, 136.0 (d, J CP = 28.5 Hz), 138.5, 147.9, 151.6 (d, J CP = 12.0 Hz), 175.1; 31 P NMR (CDCl3, 162MHz) δ: -16.4; HRMS (ESI-TOF) m / z: Calcd. for C 39 H 35 ClN2O3P [M+H] +: 645.2068;Found: 645.2075.

[0039] (II) Application of chiral pyrrolidinone-oxanthracene-triphenylphosphine ligand PI-Xan-Phos as a ligand in catalyzing asymmetric allyl alkylation reactions

[0040] The present invention relates to the chiral pyrrolizimidazolone-oxanthracene-triphenylphosphine ligand PI-Xan-Phos of formula (1). This type of ligand comprises a triphenylphosphine group, an oxanthracene group, and a chiral pyrrolizimidazolone group. The chiral pyrrolizimidazolone group provides a chiral cavity environment, the oxanthracene group provides a rigid framework, and the phosphine atom of the triphenylphosphine group is an electron-rich coordination site that can coordinate with a metal, thereby generating a chiral ligand-metal phosphine complex. This complex is used in the catalytic asymmetric allylic alkylation of alcohols. However, it should be emphasized that the chiral ligand PI-Xan-Phos of the present invention is not limited to its application as a chiral ligand in the catalytic asymmetric allylic alkylation of alcohols.

[0041] Example 1: Application of chiral ligands PI-Xan-Phos with various substituents in asymmetric catalytic reactions

[0042] To demonstrate the application value of the developed chiral ligand PI-Xan-Phos in asymmetric catalytic systems, we selected the asymmetric allyl alkylation reaction involving benzyl alcohol 3a and allyl alcohol ester 4a as the template reaction, and selected various substituted compounds PI-Xan-Phos as chiral ligands to generate chiral complexes in situ with palladium(II) to verify the asymmetric catalytic effect of the chiral ligand PI-Xan-Phos (Table 2).

[0043] Table 2 shows the application of chiral ligands PI-Xan-Phos with various substituents in asymmetric catalytic reactions.

[0044]

[0045] Experimental conclusion: The asymmetric allyl alkylation template reaction involving benzyl alcohol 3a and allyl alcohol ester 4a was selected as the evaluation index. The experimental results show that the chiral ligands PI-Xan-Phos with various substituents shown in formula (1) all exhibited asymmetric catalytic effects in the asymmetric allyl alkylation reaction involving benzyl alcohol 3a and allyl alcohol ester 4a, and can be developed into a new dominant chiral pyrrolizimidazolone-oxanthracene-triphenylphosphine ligand PI-Xan-Phos, which is worthy of further in-depth research.

[0046] Example 2: Application of chiral ligand PI-Xan-Phos-3 in asymmetric catalytic reactions

[0047] To demonstrate the application value of the developed chiral ligand PI-Xan-Phos-3 in asymmetric catalytic systems, we selected asymmetric allyl alkylation reactions involving various substituents of alcohol 3 and various substituents of allyl alcohol ester 4 as template reactions to verify the catalytic effect of chiral ligand PI-Xan-Phos-3 (Table 3).

[0048] Table 3 shows the application of the chiral ligand PI-Xan-Phos-3 in asymmetric catalytic reactions.

[0049]

[0050] Experimental conclusion: The asymmetric allyl alkylation reaction involving various substituents of alcohol 3 and allyl alcohol ester 4 was selected as the evaluation index. The experimental results show that the chiral ligand PI-Xan-Phos-3 shown in formula (1) generates a chiral palladium complex in situ with [Pd(C3H5)Cl]2, which shows asymmetric catalytic effect in the asymmetric allyl alkylation reaction involving various substituents of alcohol 3 and allyl alcohol ester 4. It can be developed into a new dominant chiral ligand PI-Xan-Phos, which is worthy of further in-depth research.

[0051] Example 3: Application of chiral ligand PI-Xan-Phos-3 in asymmetric catalytic reactions

[0052] To demonstrate the application value of the developed chiral ligand PI-Xan-Phos-3 in asymmetric catalytic systems, we selected asymmetric allyl alkylation reactions involving malonate 6 with various substituents and allyl alcohol ester 4 with various substituents as template reactions to verify the catalytic effect of chiral ligand PI-Xan-Phos-3 (Table 4).

[0053] Table 4 shows the application of the chiral ligand PI-Xan-Phos-3 in asymmetric catalytic reactions.

[0054]

[0055] Experimental conclusions: Asymmetric allyl alkylation reactions involving various substituents of malonate 6 and allyl alcohol ester 4 were selected as evaluation indicators. Experimental results show that the chiral ligand PI-Xan-Phos-3 shown in formula (1) reacts in situ with [Pd(C3H5)Cl]2 to form a chiral palladium complex, exhibiting asymmetric catalytic effects in the asymmetric allyl alkylation reactions involving various substituents of malonate 6 and allyl alcohol ester 4. It can be developed into a new dominant chiral ligand PI-Xan-Phos, which warrants further in-depth research.

Claims

1. A chiral pyrroloimidazole-oxanthracene-triphenylphosphine ligand PI-Xan-Phos, characterized in that: The compound has the structure shown in general formula (Ⅰ); （I）； In the formula, R 1 It can be hydrogen, methyl, halogen, or methoxy; R 2 It can be hydrogen or hydroxyl; Specifically, it is one of the following structural formulas: 。 2. A method for preparing the chiral pyrroloimidazole-oxanthracene-triphenylphosphine ligand PI-Xan-Phos as described in claim 1, characterized in that: The corresponding prolyl arylamine 1 undergoes a condensation reaction with triphenylphosphine-based oxanthracene formaldehyde 2 to generate the target product, chiral pyrrolizimidazolone-oxanthracene-triphenylphosphine ligand PI-Xan-Phos. The synthesis route is as follows: 。 3. The use of the chiral pyrrolipidazolone-oxanthracene-triphenylphosphine ligand PI-Xan-Phos as described in claim 1 as a ligand-catalyzed asymmetric allyl alkylation reaction.

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