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Bridged bis-Schiff-base-titanium complex, and synthesis method and application thereof

A double Schiff base, titanium complex technology, applied in titanium organic compounds, asymmetric synthesis, organic compounds/hydrides/coordination complex catalysts, etc., can solve the problems of reduced catalytic activity and enantioselectivity , to achieve the effect of improving activity and enantioselectivity

Inactive Publication Date: 2011-11-09
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Studies have found that the structure of this type of catalyst is a dimer structure, which is easily dissociated into a Salen-Ti monomer structure without catalytic activity in solution, resulting in a decrease in catalytic activity and enantioselectivity [Belokon, Y.N.; Blacker, A.J.; Carta, P.; Clutterbuck, L.A.; North, M. Tetrahedron 2004, 60, 10433-10447.]

Method used

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  • Bridged bis-Schiff-base-titanium complex, and synthesis method and application thereof
  • Bridged bis-Schiff-base-titanium complex, and synthesis method and application thereof
  • Bridged bis-Schiff-base-titanium complex, and synthesis method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Embodiment 1: the synthesis of double Salen ligand 7a

[0041] 1) Synthesis of compound 3a from compounds 1a and 2a

[0042] Add compound 1a (775mg, 4.0mmol, synthetic method reference to [Jacobsen, E.N.et al., J.Am.Chem.Soc.2001, 123, 2687]) and cis-5-norbornene to a 50mL three-necked flask -endo-2,3-dicarboxylic acid (363mg, 2.0mmol) and DMAP (49mg, 0.4mmol), add dichloromethane (8mL) and DMF (0.8mL) after pumping out argon, stir for 10 minutes and cool to 0°C, add DIC (0.53g, 4.2mmol) and keep stirring at 0°C for 10 minutes, rise to room temperature and stir for 72 hours, TLC detects that the reaction is complete, add dichloromethane (50mL) to the reaction solution, add 0.1M hydrochloric acid (20mL) Washing, saturated aqueous NaCl washing (3 × 30mL), anhydrous NaCl 2 SO 4 After drying, it was filtered, and the solvent was removed under reduced pressure. It was separated by column chromatography (petroleum ether: ethyl acetate = 8:1) to obtain 0.816 g of a white so...

Embodiment 2

[0047] Embodiment 2: the synthesis of compound 7b

[0048] Add dropwise the chloroform solution (800mg, 1.44mmol, in 20mL) of 3b (synthetic method is the same as 3a) to the solution of 6a, rise to room temperature after the dropwise addition, add Molecular sieves were stirred for 48 hours, filtered and washed with dichloromethane, the solvent was removed under reduced pressure, and column chromatography (petroleum ether: ethyl acetate = 20:1) gave 320 mg of a yellow foamy solid. Yield 63%; m.p.169-170°C; [α] D 20 =-231.7 (c=0.51, CHCl 3 ); 1 H NMR (300MHz, CDCl 3 )δ1.26(s, 18H), 1.41(s, 18H), 1.44(s, 18H), 1.47-1.52(m, 3H), 1.71-1.78(m, 5H), 1.89-2.00(m, 8H) , 3.35-3.38(m, 4H), 6.94(d, 2H, J=2.7Hz), 7.01(d, 2H, J=2.4Hz), 7.10(d, 2H, J=2.7Hz), 7.34(d, 2H, J=2.4Hz), 7.66(t, 1H, J=7.8Hz), 8.29(s, 2H), 8.34(s, 2H), 8.42(dd, 2H, J=7.6, 1.6Hz), 8.95( s, 1H), 13.65 (br, 2H), 13.99 (br, 2H) ppm; 13 C NMR (75MHz, CDCl 3 )δ 24.2, 29.1, 29.4, 31.4, 33.1, 33.2, 34.0, 34.9, 72....

Embodiment 3

[0049] Embodiment 3: the synthesis of compound 7c

[0050] Add dropwise the chloroform solution (1.2g in 30mL) of 3c (synthetic method is the same as 3a) to the solution of 6a, rise to room temperature after the dropwise addition, add Molecular sieves were stirred for 48 hours, filtered and washed with dichloromethane, the solvent was removed under reduced pressure, and column chromatography (petroleum ether: ethyl acetate = 25:1) gave 380 mg of a yellow foamy solid. Yield 37%; m.p. 170-172°C; [α] D 20 =-204.1 (c=0.50, CHCl 3 ); 1 H NMR (300MHz, CDCl 3 )δ1.19(s, 18H), 1.30(s, 18H), 1.34(s, 18H), 1.41-1.48(m, 6H), 1.67(s, 6H), 1.89-2.05(m, 10H), 3.28- 3.30(m, 4H), 6.71(d, 2H, J=2.7Hz), 6.89(d, 2H, J=2.1Hz), 7.03(d, 2H, J=2.1Hz), 7.19(t, 2H, J =7.9Hz), 7.26(d, 2H, J=3.0Hz), 7.61(dd, 2H, J=8.1, 1.2Hz), 7.74(dd, 2H, 7.8, 1.5Hz), 7.91(s, 2H), 8.27 (s, 2H), 13.56 (br, 2H), 13.89 (br, 2H) ppm; 13 C NMR (75MHz, CDCl 3 )δ24.2, 29.1, 29.3, 31.3, 31.6, 32.8, 33.0, 33.9, 34.4,...

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Abstract

The invention relates to a novel bridged bis-Schiff base ligand, a bridged bis-Schiff-base-titanium complex, a synthesis method of the complex and application of the complex in the cyanidation reaction of various carbonyl compounds. The bridged bis-Schiff-base-titanium complex provided by the invention presents very high catalytic activity and excellent enantioselectivity in the asymmetric cyanidation of aldehydes.

Description

technical field [0001] The invention relates to a novel bridging double Schiff base (Salen) ligand and a bridging double Schiff base-titanium complex, as well as a synthesis method and application of the complex. The complex can be used in the cyanation reaction of various carbonyl compounds, especially in the asymmetric cyanation reaction of various aldehyde compounds, and can achieve ideal stereoselectivity and conversion rate under mild conditions. Background technique [0002] Cyanohydrins, especially chiral cyanohydrins, contain two functional groups, cyano and hydroxyl, and can be transformed into a variety of bifunctional compounds, such as α-hydroxy carboxylic acids, α-amino acids, α-hydroxy aldehydes or ketones, and β-amino groups. Alcohols, etc., are a very important class of organic synthesis intermediates, widely found in medicine and pesticides [North, M.; Usanov, D.L; Young, C.Chem.Rev.108, 5146-5226(2008)]. The asymmetric addition reaction of cyanide reagents...

Claims

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Application Information

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IPC IPC(8): C07F7/28C07B43/08C07B53/00B01J31/22C07C251/24C07D311/82C07D213/79C07C255/38C07C255/57C07C253/30C07C253/08C07F7/18
Inventor 丁奎岭张志鹏王正张如周
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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