N-aryl axially chiral carbene-oxazoline compound and application thereof

A compound and axial chiral technology, applied in the field of N-aryl axial chiral carbene-oxazoline compounds, to achieve the effect of expanding design ideas

Inactive Publication Date: 2011-06-15
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] However, so far, no axial chiral compounds with N-aryl bonds have been applied in the design and development of axial chiral ligands.

Method used

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  • N-aryl axially chiral carbene-oxazoline compound and application thereof
  • N-aryl axially chiral carbene-oxazoline compound and application thereof
  • N-aryl axially chiral carbene-oxazoline compound and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] (1) Under an ice bath, thionyl chloride was slowly added dropwise by 1mol in 10ml methanol solution of 0.2mol 1-hydroxyl-2-naphthoic acid, heated to reflux temperature after rising to room temperature, TLC (PE: EA(v / v) is 20:1, R f = 0.4) monitor the complete reaction; washing, drying, concentration, column chromatography (PE: EA (v / v) is 40: 1) to obtain compound IV-1; the yield is 69%;

[0047] 1 H NMR (CDCl 3 , 400MHz) δ3.98(s, 3H), 7.27(d, J=10Hz, 1H), 7.52(d, J=5Hz, 1H), 7.60(d, J=6Hz, 1H), 7.75-7.76(m , 2H), 8.42(d, J=4Hz, 1H), 11.99(s, 1H);

[0048] (2) 0.4mol pyridine was added to 0.2mol compound IV-1 in 8ml dichloromethane solution; Under ice bath, 0.6mol trifluoromethanesulfonic anhydride was slowly dripped into the solution, reacted at room temperature for three hours, TLC (PE : EA(v / v) is 10:1, R f =0.4) Monitor compound IV-1 reaction complete; After washing, drying, concentrating, column chromatography (eluent is PE: EA (v / v) is 40:1, 20:1 and 10:1) ob...

Embodiment 2

[0071] Preparation of palladium complex:

[0072] 8ml tetrahydrofuran was added to the reaction tube that 0.2mol compound Ia-1, 0.2mol palladium acetate and 0.4mol potassium iodide were housed, reflux reaction 12 hours, TLC (developing agent is dichloromethane (DCM), R f =0.5) It is monitored that the reaction of raw materials is complete, washed with water, dried, concentrated, column chromatography (eluent is PE: DCM (v / v)=6: 1 and DCM) to obtain compound IIa-Pd, its X-Ray figure Such as figure 1 As shown, the yield was 80%.

[0073]

[0074] Compound IIa-Pd

[0075] Compound IIa-Pd: 1 H NMR (400MHz, CDCl 3 , TMS) δ3.46 (s, 3H), 4.63 (dd, J 1 =6Hz,J 2 =10Hz, 1H), 5.06(t, J=10Hz, 1H), 6.13(dd, J 1 =6Hz,J 2 =10Hz, 1H), 6.64(d, J=8Hz, 1H), 6.92(d, J=7Hz, 2H), 7.14-7.23(m, 3H), 7.37-7.43(m, 4H), 7.49(t, J=8Hz, 1H), 7.70(t, J=8Hz, 1H), 7.96(d, J=8Hz, 1H), 8.11(d, J=8Hz, 1H), 8.29(d, J=9Hz, 1H) .

Embodiment 3

[0077] Preparation of gold complexes:

[0078] 8ml of acetonitrile was added to the reactor equipped with 0.1mol compound Ia-1 and compound Ib-1, 0.1mol dimethyl sulfide gold chloride and 0.2mol sodium acetate respectively, reacted at room temperature for 24 hours, TLC (developing agent PE: DCM (v / v) is 3:1, R f =0.25) to monitor that the reaction of the raw material is complete, after concentration, column chromatography (eluent is PE: DCM (v / v)=6:1 and 3:1) to obtain compound IIa-Au and compound IIb-Au; two The yields of the two configurations were 95% and 45%, respectively.

[0079]

[0080] Compound IIa-Au: 1 H NMR (400MHz, CDCl 3 , TMS) δ3.87 (t, J=9Hz, 1H), 4.16 (s, 3H), 4.45 (dd, J 1 =8Hz,J 2 =10Hz, 1H), 5.15(t, J=10Hz, 1H), 6.73-6.76(m, 2H), 6.89(d, J=8Hz, 1H), 7.16-7.17(m, 3H), 7.31-7.38( m, 2H), 7.47-7.54(m, 3H), 7.65(t, J=8Hz, 1H), 8.03(d, J=8Hz, 1H), 8.14-8.28(m, 2H), [α] 20 D +33.0 (c 0.2, CHCl 3 ); its X-Ray diagram is as follows figure 2 shown;

...

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Abstract

The invention relates to a non-carbon-carbon aryl axially chiral compound and application thereof. The invention discloses a novel N-aryl axially chiral carbene-oxazoline compound (compound disclosed as formula I or an optical isomer thereof), and synthesizes a series of metal complexes (compounds disclosed as formula II) by using the N-aryl axially chiral carbene-oxazoline compound as the ligand. The obtained metal complexes can be used for catalyzing the asymmetric allylic substitution reaction, and achieves a good effect. The invention breaks through the design and development concept of the existing axially chiral ligand, and widens the design thought of the existing axially chiral ligand.

Description

technical field [0001] The invention relates to a non-carbon-carbon aryl axis chiral compound and its application, in particular to an N-aryl axis chiral carbene-oxazoline compound and its application. Background technique [0002] The N-aryl bond axis chiral compounds (such as metolachlor, alachlor, acetochlor, pretilachlor, propisochlor and butachlor, etc.) reported in the early literature are widely used in pesticides and herbicides. For example, metolachlor with N-aryl chiral axis and central chiral carbon developed by Ciba-Geigy Corporation (now owned by Syngenta Corporation) in the early 1970s is a kind of It is a multi-selective herbicide with low toxicity to humans and animals and high quality. The chlorinated acetamide herbicides with similar structures widely recognized by the market currently mainly include six kinds of alachlor, acetochlor, pretilachlor, butachlor, propachlor, and metolachlor. Herbicides play an important role in modern farmland chemical weed c...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B53/00C07C49/403B01J31/22C07D413/10C07C45/68C07F1/12C07F15/00
Inventor 王飞军李升可屈明亮张睿徐琴施敏
Owner EAST CHINA UNIV OF SCI & TECH
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