Multidentate oxazoline ligand having chirality and its compounding product with main group metal or transition metal, synthesis method and its use

A multidentate oxazoline and transition metal technology, which is applied in the field of catalytic asymmetric synthesis, can solve the problems of tediousness, failure to obtain good results, troublesome operation, etc.

Inactive Publication Date: 2004-07-21
SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] But in the vast majority of cases, only the expensive tert-butyl substituted (R=tert-Bu) Bisoxazoline can achieve good results; and copper salts also require water-sensitive copper trifluoromethanesulfonate, or require It is cumbersome to obtain copper hexafluoroantimonate from the reaction of light-sensitive silver hexafluoroantimonate and anhydrous copper chloride
This makes the catalyst very expensive and at the same time cumbersome to operate
[0006] With the expansion of the application range, even the complexes of tert-Butyl-Bisoxazoline / Cu(II) cannot achieve good results in some new reactions

Method used

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  • Multidentate oxazoline ligand having chirality and its compounding product with main group metal or transition metal, synthesis method and its use
  • Multidentate oxazoline ligand having chirality and its compounding product with main group metal or transition metal, synthesis method and its use
  • Multidentate oxazoline ligand having chirality and its compounding product with main group metal or transition metal, synthesis method and its use

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0099] Ligand L 1 Synthesis:

[0100]

[0101] Add 3.72g 1 (17mmol) and L-Valinol 7.04g (68mmol) to a 25ml Schlenk bottle, heat up to 80°C, the reaction system becomes a homogeneous transparent solution, stir, every 12 hours of heating, cool to 30°C, then vacuum methanol for about One hour, the cumulative reaction is 80 hours. Stop the reaction, dissolve with a small amount of dichloromethane, and perform direct flash chromatography with eluent (ethyl acetate / methanol=30 / 1) to obtain 4.52 g of product S1 as a white solid, with a yield of 61%. [α] D 20 =20.5° (c=1.09, HCl 3 ); 1 H NMR (300MHz, CDCl 3 ): δ0.93(m, 18H), 1.60(s, 3H), 1.65-1.90(m, 3H), 2.50(ABd, J=14.1Hz, 1H), 3.25(ABd, J=14.1Hz, 1H) , 3.32-3.42(m, 1H), 3.45-3.65(m, 3H), 3.67-3.90(m, 8h), 6.93(d, J=9.2Hz, 1H), 8.2(d, J=9.0Hz, 1H ), 8.8(d, J=8.1Hz, 1H); 13 C NMR (75MHz, CDCl 3 ): 174.33, 173.44, 173.30, 63.39, 62.90, 62.73, 60.424, 57.51, 57.23, 57.11, 53.752, 42.87, 29.43, 29.18, 29.10, 27.21, 27.14, 1...

Embodiment 2

[0104] Ligand L 2 Synthesis:

[0105]

[0106] Add 2.45g (11.2mmol) 1, 5.2g (45.0mmol) of L-Isoleucinol to a 25ml Schlenk bottle, heat up to 70°C, the reaction system becomes a homogeneous transparent solution, stir, every 12 hours of heating, cool to 30°C and vacuum pump Methanol is about one hour, and the cumulative reaction is 80 hours. Stop the reaction, after dissolving with a small amount of dichloromethane, directly flash chromatography, eluent (ethyl acetate / methanol=30 / 1), get the product S 2 It is 2.26 g of white solid, and the yield is 43.5%. 1 H NMR (300MHz, CDCl 3 ): δ0.94(m, 18H), 1.05-1.12(m, 3H), 1.38-1.58(m, 6H), 1.58(s, 3H), 1.90(br, 3H), 2.49(ABd, J=14.1 Hz, 1H), 3.22(ABd, J=14.1Hz, 1H), 3.3-4.0(m, 9H), 6.95(d, J=8.2Hz, 1H), 8.18(d, J=8.6Hz, 1H), 8.86 (d, J=9.2Hz, 1H). MS (m / z): 474 (M+1) + , (2), 357, (100), 313(67), 295(48), 69(40), 41(34), 55(26), 196(24), 339(24).

[0107] Add S to the 50ml three-necked bottle 2 750mg (1.6mmol), triphenylphos...

Embodiment 3

[0109] Ligand L 3 Synthesis:

[0110]

[0111] Add 1.33g (6.1mmol) 3.72g (27mmol) of 1,D-phenylglycinol to a 25ml Schlenk bottle, heat up to 90°C, the reaction system becomes a homogeneous transparent solution, stir, and cool to 30°C every 12 hours of heating After that, the methanol was vacuumed for about one hour, and the cumulative reaction was 60 hours. Stop the reaction, dissolve with a small amount of dichloromethane, and perform direct flash chromatography with an eluent (ethyl acetate / methanol=25 / 1) to obtain 1.06 g of product S3 as a white solid, with a yield of 32.6%. [α] D 20 =-102.3° (c=1.14, HCl 3 ); 1 H NMR (300MHz, CDCl 3 ): δ1.54(s, 3H); 1.63(br, s, 3H), 2.63(ABd, J=15.0Hz, 1H), 3.2(AB, J=15.0Hz, 1H), 3.6-4.1(m, 6H), 5.1-5.28(m, 3H), 7.28(m, 15H), 7.47(d, J=9.5Hz, 1H), 8.63(d, J=8.1Hz, 1H), 9.45(d, J=8.3 , 1H), 13 CNMR (75MHz, CDCl 3 ):173.6,173.1,172.7,138.6,138.4,128.73,128.66,127.7,127.6,126.73,126.71,126.43,66.43,65.69,65.51,56.05,55.60,53.38,4...

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Abstract

A chiral multi-tooth oxazoline ligand, its matches with primary-family metals or transition metals, its synthesizing process, and its application in asymmetrical catalytic synthesis are disclosed.

Description

technical field [0001] The invention relates to a class of chiral multidentate oxazoline ligands and their complexes with main group metals or transition metals from the third group to the thirteenth group, the synthesis method and its application in catalytic asymmetric synthesis. Background technique [0002] It is well known that the enantioselectivity and reactivity of asymmetric catalytic reactions mainly depend on the nature of the catalyst, which is largely determined by the nature of the chiral ligand. Therefore, designing and synthesizing a class of effective chiral ligands is often the key to the success of asymmetric reactions. have C 2 - Symmetrical bisoxazoline ligands are a relatively important class of ligands: since ligands containing an oxazoline ring were first used in asymmetric catalysis in 1986, countless ligands containing at least one oxazoline ring The body was synthesized and successfully applied to a series of organometallic catalyzed reactions in...

Claims

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Application Information

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IPC IPC(8): C07D263/14
Inventor 唐勇周剑
Owner SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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