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Chiral bisoxazoline-alkynyl phosphine ligand as well as preparation and application thereof

A technology of bisoxazoline and alkynyl phosphine, which is applied to chiral bisoxazoline-alkynyl phosphine ligands and the fields of preparation and application thereof, can solve the problems of ineffective catalytic reaction and high enantioselectivity, and achieves The chiral raw materials are easy to obtain, the chiral raw materials are simple, and the reaction yield is high.

Active Publication Date: 2022-03-15
SHANGHAI JIAO TONG UNIV
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

Chiral bisoxazoline-phenylphosphine ligands in the prior art can achieve transition metal-catalyzed asymmetric allyl substitution reactions with high selectivity [(a) Yamaishi, T.; Ohnuki, M.; Kiyooka, T .; Masui, D.; Sato, K.; Yamaguchi, M. Tetrahedron: Asymmetry 2003, 14, 3275. (b) Ghor ai, S.; Chirke, S.S.; Xu, W.-B.; Chen, J. -F.; Li, C.J.Am.Chem.Soc.2019, 141, 11430. (c) Ghorai, S.; Rehman, S.U.; .Org.Lett.2020,22,3519-3523.) and asymmetric addition reaction of terminal alkyne to isatin [Chen,J.-F.; Li,C.Org.Lett.2020,22,4686.] .However, the types of reactions applicable to this kind of ligands are limited. Due to the large steric hindrance of the benzene ring connected to the phosphine atom, there is repulsion between the phosphine atom and the multi-substituted allyl substrate, which cannot effectively catalyze the reaction and achieve a high reaction rate. Enantioselectivity. In addition, such ligands cannot achieve the required remote control in reactions such as desymmetry

Method used

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  • Chiral bisoxazoline-alkynyl phosphine ligand as well as preparation and application thereof
  • Chiral bisoxazoline-alkynyl phosphine ligand as well as preparation and application thereof
  • Chiral bisoxazoline-alkynyl phosphine ligand as well as preparation and application thereof

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preparation example Construction

[0031] Described preparation method comprises the steps:

[0032]

[0033] The 2-(2-bromophenyl)oxazoline 3 used in the present invention was prepared by referring to literature. Specifically, R 1 For isopropyl (Examples 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10) and tert-butyl (Examples 11 and 12), refer to Jin, Y.; Du, D. - M. Tetrahedron, 2012, 68, 3633. When R 1 For phenyl (Example 18), refer to Liu, W.; Ali, S.Z.; Ammann, S.E.; White, M.C.J.Am.Chem.Soc.2018, 140, 10658. When R 1 For cyclohexyl (13, 14 and 15), refer to Tani, K; Behenna, D.C.; McFadden, R.M.; Stoltz, B.M.Org. Lett.2007, 9, 2529. When R1 is methyl (Example 16), refer to Kim, K.S.; Moon, C.W.; Hong, J.K.; Kim, J.H.Bull.Korean.Chem.Soc.2001, 22, 237. When R 1 For ethyl (Example 17), refer to Tang, X.; Zhang, D.; Jie, S.; Sun, W.-H.;

[0034] The terminal alkyne 5 used in the present invention is commercially available.

[0035] Preparation method of the present invention can be further embodied as follows ...

Embodiment 1

[0039] Preparation of chiral bisoxazoline-alkynylphosphine ligand 1a (R1 = isopropyl; R2 = phenyl).

[0040] Yield, 61%; m.p.237.5-239.2°C; 1 H NMR (400MHz, Chloroform-d) δ7.95–7.89(m,3H),7.59–7.53(m,1H),7.51–7.46(m,2H),7.46–7.41(m,2H),7.39–7.34 (m,2H),7.34–7.29(m,3H),4.52–4.26(m,2H),4.16–3.91(m,4H),1.84–1.78(m,1H),1.72–1.59(m,1H) ,1.04(d,J=6.7Hz,3H),0.93(d,J=6.7Hz,3H),0.83(d,J=6.7Hz,3H),0.73(d,J=6.7Hz,3H); 13 C NMR (101MHz, CDCl 3 )δ163.1(d, J=3.0Hz), 162.7(d, J=3.0Hz), 138.9(d, J=19.2Hz), 138.3(d, J=20.2Hz), 134.2, 133.3, 131.72, 131.70 ,131.5(d,J=24.2Hz),131.1(d,J=22.2Hz),130.3,130.3,129.6(d,J=4.0Hz),129.4(d,J=4.0Hz),128.3,128.2,128.1 ,128.0,123.7(d,J=2.0Hz),105.9,90.0(d,J=24.2Hz),73.1,73.0,70.3,70.2,33.0,32.8,19.0,18.8,18.5,18.3. 31 P NMR (162MHz, CDCl 3 )δ-36.6. HRMS (ESI) calcd for C 32 h 33 N 2 o 2 PH([M+H]):509.2352. Found: 509.2355.

Embodiment 2

[0042] Preparation of chiral bisoxazoline-alkynylphosphine ligand 1b (R1 = isopropyl; R2 = methyl).

[0043] Yield, 52%; m.p.222.1-223.8°C; 1 H NMR (400MHz, Chloroform-d) δ7.89–7.66(m,2H),7.48–7.09(m,6H),4.31–4.21(m,1H),4.20–4.13(m,1H),4.05–3.81 (m,4H),1.79–1.61(m,5H),0.98(d,J=6.7Hz,3H),0.92(d,J=6.7Hz,3H),0.87(d,J=6.7Hz,3H) ,0.81(d,J=6.7Hz,3H). 13 C NMR (101MHz, CDCl 3 )δ163.2(d, J=2.0Hz), 162.9(d, J=3.0Hz), 139.4(d, J=19.2Hz), 138.9(d, J=21.2Hz), 133.9, 133.2, 131.4(d ,J=23.2Hz),131.1(d,J=23.2Hz),130.5,130.3,129.5(d,J=4.0Hz),129.4(d,J=3.0Hz),128.1,127.9,103.9,78.2(d ,J=17.2Hz),77.3,73.0,72.9,70.2,70.1,33.0,32.7,19.0,18.8,18.4,18.1,5.7(d,J=2.0Hz). 31 P NMR (162MHz, CDCl 3 )δ-35.8. HRMS (ESI) calcd for C 27 h 31 N 2 o 2 PH([M+H]):447.2196. Found: 447.2189.

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Abstract

The invention discloses a chiral bisoxazoline-alkynyl phosphine ligand as well as preparation and application of the chiral bisoxazoline-alkynyl phosphine ligand. Starting from 2-oxazoline substituted bromobenzene, terminal alkyne and triphenoxy phosphine, high-efficiency and high-yield preparation of the ligand is realized. The ligands can be used for but not limited to asymmetric reactions in which metals such as rhodium and cobalt participate, and are used for preparing 1, 2-disubstituted allylamine, chiral pyridine and the like with high enantioselectivity.

Description

technical field [0001] The invention belongs to the technical field of chemistry and chemical engineering, and relates to a preparation method of a chiral compound, in particular to a chiral bisoxazoline-alkynylphosphine ligand and its preparation and application. Background technique [0002] Transition metal-catalyzed asymmetric transformation is one of the effective methods for the synthesis of chiral compounds, and chiral ligands are the key to realize asymmetric metal catalysis, in order to improve the reactivity, change the chemical selectivity of the reaction and realize the high enantiometry of the product. selective. [0003] Chiral tridentate ligands can reduce the degree of freedom of the metal center, which is beneficial to improve the enantioselectivity of reactions catalyzed by metals such as cobalt and rhodium. Chiral bisoxazoline-phenylphosphine ligands in the prior art can achieve transition metal-catalyzed asymmetric allyl substitution reactions with high ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/653B01J31/24C07C213/08C07C217/84C07D471/10
CPCC07F9/653B01J31/2404C07C213/08C07D471/10C07B2200/07B01J2531/821B01J2531/0261B01J2531/0244B01J2231/34B01J2231/44C07C217/84Y02P20/584
Inventor 李长坤李冰徐文斌孙明河
Owner SHANGHAI JIAO TONG UNIV
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