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Chiral compound comprising iminopyridyl oxazoline and preparation method thereof

A technology containing imine pyridine oxazoline and compound is applied in the field of synthesizing imine pyridine oxazoline-containing compound, can solve problems such as asymmetry, and achieve the effect of high chemical conversion rate

Active Publication Date: 2015-03-25
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although it has good catalytic activity, its asymmetric catalytic

Method used

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  • Chiral compound comprising iminopyridyl oxazoline and preparation method thereof
  • Chiral compound comprising iminopyridyl oxazoline and preparation method thereof
  • Chiral compound comprising iminopyridyl oxazoline and preparation method thereof

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Experimental program
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Effect test

Embodiment

[0065] Embodiment: Amine formula (3) is commercially available, and 2-bromo-6-acylpyridine formula (2) is according to literature (Ruifa Zong, Dong Wang, Richard Hammitt, and RandolphP.Thummel.J.Org.Chem. , 2006,71,167) prepared. Oxazoline ring formula (5) according to literature ((a) Bandyopadhyay, S.; Zhou, W.; Breslow, R.Org. Lett.2007, 9, 1009; (b) Levine, M.; Kenesky, C.S.; Zheng, S.; Quinn, J.; Breslow, R. Tetrahedron Lett. 2008, 49, 5746.) Preparation.

[0066] Preparation of 2-bromo-6-iminopyridine formula (4)

example A1

[0067] Example A1: Preparation of 2-bromo-6-iminopyridine A1

[0068]

[0069] 2,6-Dimethylaniline (2.9083g, 24mmol, 1.2equiv) and 2-bromo-6-acetylpyridine (4.0006g, 20mmol, 1.0equiv) were dissolved in 50mL of toluene, p-toluenesulfonic acid (0.0760g, 0.4mmol, 2mol%), reacted for 24h, and recrystallized from ethanol to obtain 4.7901g (15.8mmol, 79%) of 2-bromo-6-iminopyridine A1.

[0070] 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 C NMR (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

[0071] Example A2: Preparation of 2-bromo-6-iminopyridine A2

[0072]

[0073] 2,6-Diethylaniline (3.5815g, 24mmol, 1.2equiv) and 2-bromo-6-acetylpyridine (4.0006g, 20mmol, 1.0equiv) were dissolved in 50mL of toluene, p-toluenesulfonic acid (0.0760g, 0.4mmol, 2mol%) catalyzed, reacted for 24h, recrystallized from ethanol to obtain 5.5341g (16.7mmol, 84%) 2-bromo-6-iminopyridine A2.

[0074] 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=7.5Hz, 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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PUM

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Abstract

The invention discloses a synthetic compound comprising iminopyridyl oxazoline, a preparation method thereof, a metal complex of the compound and application of a prochiral organic compound which contains at least one carbon / carbon or carbon / heteroatomic double bond in hydroboration. According to the compound, the total yield of two steps of a high-efficiency synthetic route can reach 50%, and the metal complex is an excellent catalyst or a catalyst precursor which is used for asymmetric synthesis (such as asymmetric hydrogenation of prochiral, unsaturated and organic compounds). The invention also provides application of the metal complex as a homogeneous catalyst. The catalyst is used for preparing a chiral organic compound by being subjected to the hydroboration and hydrosilation asymmetric addition on the carbon or carbon heteroatomic double bond of the prochiral organic compound, and an ee value can be more than 90%.

Description

technical field [0001] The present invention relates to the synthesis of imine-containing pyridine oxazoline compounds and processes for their preparation, metal complexes of such compounds and the hydroboration of prochiral organic compounds containing at least one carbon / carbon or carbon / heteroatom double bond use in . Background technique [0002] The asymmetric reactions catalyzed by transition metal complexes have attracted extensive attention from academia and industry around the world, and the research on the ligands connected to the central metal is also very extensive. Among them, bisoxazoline (Box) ligands, 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.Organometallics1989,8,846.], followed by pyridine bisoxazoline ligands received great attention [(a) Dalit Rechavi and Marc Lemaire.Chem.Rev., 2002,102(10), pp3467–3494.( b)...

Claims

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Application Information

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IPC IPC(8): C07D413/04C07F15/03B01J31/22C07F5/04C07C29/143C07C33/22C07C33/20C07C67/317C07C69/612C07B53/00
CPCB01J31/182B01J2531/842B01J2531/845C07B53/00C07B2200/07C07C29/143C07C33/22C07C67/317C07D413/04C07F5/04C07F15/03C07F15/065C07C33/20C07C69/612
Inventor 陆展席拓陈建辉
Owner ZHEJIANG UNIV
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