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A chiral compound containing aminomethylpyridine oxazoline and its preparation method

A kind of technology containing amine methyl pyridine oxazoline and compound, which is applied in the field of compound and its preparation, and achieves the effect of high chemical conversion rate

Active Publication Date: 2019-01-18
ZHEJIANG UNIV
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Problems solved by technology

[0003] In recent years, aminomethylpyridine ligands have also attracted people's attention. In 2006, Gabriel García-Herbosa reported the synthesis of aminomethylpyridine compounds and metal ruthenium complexes [Gabriel García-Herbosa, Javier Gómez, et al. al, Inorg.Chem.2006,45,pp 2483.], in 2007, complexes of aminomethylpyridine compounds and metal zirconium and hafnium also received attention [Gerhard Erker, Katrin Nienkemper, Gerald Kehr, SedaKehr, and Roland J.Organomet.Chem.2008,693,pp1572.], in 2012, Qing Wu's research group reported that the complexes of aminomethylpyridine compounds and metal nickel catalyzed the polymerization of olefins [Qing Wu, Shaobo Zai, Haiyang Gao, Zengfang Huang, Haibin Hu, and Han Wu.ACS Catal.2012,2,pp 433.], although it has good catalytic activity, it has not been reported in the asymmetric catalytic neighborhood

Method used

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  • A chiral compound containing aminomethylpyridine oxazoline and its preparation method
  • A chiral compound containing aminomethylpyridine oxazoline and its preparation method
  • A chiral compound containing aminomethylpyridine oxazoline and its preparation method

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Embodiment

[0050] Example: The amine formula (3) is commercially available, and the 2-bromo-6-acylpyridine formula (2) is in accordance with the literature (Ruifa Zong, Dong Wang, Richard Hammitt, and Randolph P. Thumbel. J. Org. Chem ., 2006, 71, 167) preparation. Aluminum reagent (R 3 ) 3 Al formula (5) is commercially available, and the aminomethylpyridine compound formula (6) is in accordance with the literature (Qing Wu, ShaoboZai, Haiyang Gao, Zengfang Huang, Haibin Hu, and Han Wu.ACS Catal.2012, 2, pp 433-440.) Preparation. The oxazoline cyclic formula (7) is according to literature ((a) Bandyopadhyay, S.; Zhou, W.; Breslow, R. Org. Lett. 2007, 9, 1009; (b) Levine, M.; Kenesky, CS; Zheng, S.; Quinn, J.; Breslow, R. Tetrahedron Lett. 2008, 49, 5746.).

[0051] A) Preparation of 2-bromo-6-imine pyridine formula (4)

example A1

[0052] Example A1: Preparation of 2-bromo-6-iminopyridine A1

[0053]

[0054] 2,6-Dimethylaniline (2.9083g, 24mmol, 1.2equiv) and 2-bromo-6-acetylpyridine (4.0006g, 20mmol, 1.0equiv) dissolved in 50mL toluene, p-toluenesulfonic acid (0.0760g, 0.4mmol, 2mol%) catalyzed, reacted for 24h, and recrystallized from ethanol to obtain 4.7901g (15.8mmol, 79%) 2-bromo-6-iminopyridine A1.

[0055] 1 H NMR(400MHz, CDCl 3 )δ8.33(d,J=7.7Hz,1H), 7.64(t,J=7.7Hz,1H), 7.56(d,J=7.7Hz,1H), 7.06(d,J=7.5Hz,2H) ,6.93(t,J=7.5Hz,1H), 2.15(s,3H), 2.01(s,6H). 13 CNMR(100MHz, CDCl 3 )δ166.15,157.44,148.44,140.97,138.74,129.25,127.95,125.25,123.26,120.03,17.90,16.63.

example A2

[0056] Example A2: Preparation of 2-bromo-6-iminopyridine A2

[0057]

[0058] 2,6-Diethylaniline (3.5815g, 24mmol, 1.2equiv) and 2-bromo-6-acetylpyridine (4.0006g, 20mmol, 1.0equiv) dissolved in 50mL toluene, p-toluenesulfonic acid (0.0760g, 0.4mmol, 2mol%) catalyzed, reacted for 24h, ethanol recrystallized to obtain 5.5341g (16.7mmol, 84%) 2-bromo-6-iminopyridine A2.

[0059] 1 H NMR(400MHz, CDCl 3 )δ8.32(d,J=7.7Hz,1H), 7.65(t,J=7.7Hz,1H), 7.57(d,J=7.7Hz,1H), 7.25-6.98(m,3H), 2.34( m, 4H), 2.17 (s, 3H), 1.12 (t, J = 7.5 Hz, 6H). 13 C NMR(100MHz, CDCl 3 )δ165.90,157.46,147.47,140.99,138.75,131.05,129.21,125.99,123.55,119.99,24.57,16.96,13.70.calcd for m / z C 17 H 19 BrN 2 330.0732, found m / z330.0735.

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Abstract

The present invention discloses a chiral compound containing aminomethyl oxazoline pyridine and a preparation method therefor. The compound is highly optically pure, current chiral, unsaturated and organic compounds are used, highly excessive optical isomers can be introduced to the synthesis of the organic compounds, and a high chemical conversion rate can be obtained. In addition, the aminomethyl oxazoline pyridine compound can also be used for other asymmetry addition reactions or cyclization reactions. The present invention also provides an application of the aminomethyl oxazoline pyridine compound provided by the present invention; the compound is in in-situ complexation with transition metal to generate a catalyst for preparing a chiral organic compound, and by performing the asymmetry addition of hydroboration on carbon-carbon double bonds of the previous chiral organic compound, the ee value can be greater than 90 %.

Description

Technical field [0001] The present invention relates to a compound and a preparation method and application thereof. Specifically, it is a chiral aminomethylpyridine-oxazoline-containing compound and a preparation method thereof, and an in-situ complex of the compound and a metal contains at least The use of a prochiral organic compound with carbon-carbon double bond in hydroboration. Background technique [0002] The asymmetric reaction catalyzed by transition metal complexes has attracted widespread attention from academic and industrial circles worldwide. Among them, the research on the ligands connected to the central metal is also very extensive. Among them, the bisoxazoline (Box) ligand, two The oxazoline ring is connected to C2. In 1989, Nishiyama reported the first pyridine bisoxazoline ligand [Nishiyama, H.; Sakaguchi, H.; Nakamura, T.; Horihata, M.; Kondo, M.; Itoh ,K.Organometallics 1989,8,846.], and then pyridine bisoxazoline ligands received a lot of attention [(a)D...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D413/04B01J31/22C07F5/04
CPCB01J31/1815B01J2231/482B01J2531/0263B01J2531/845C07D413/04C07F5/04
Inventor 陆展张何义
Owner ZHEJIANG UNIV
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