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Spiro bisimine and preparation method and application thereof

A bis-imine, bis-imine copper technology, applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, organic chemistry, etc., can solve the problems of lack of chiral catalysts and no ideal results.

Inactive Publication Date: 2009-09-02
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
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Problems solved by technology

Although asymmetric catalysis has made great progress, there are still many widely used organic reactions, such as the metal-catalyzed asymmetric insertion reaction of carbene to heteroatom-hydrogen bond (X-H), and there has been a lack of effective chiral catalysts ( Doyle, M.P. Modern Catalytic Methods for Organic Synthesis with Diazo compounds, Wiley: New York, 1998.)
Transition metal-catalyzed asymmetric insertion of carbene into silicon-hydrogen bonds is an effective method for the synthesis of chiral silicon compounds. In order to achieve asymmetric induction of this reaction, many chiral ligands and catalysts have been developed, but there are only two cases Chiral bis-rhodium catalysts can obtain higher enantioselectivity to special substrates, while other more cheap and easy-to-obtain metal catalysts, such as chiral copper catalysts, have not achieved ideal results so far (Davies, H.M.L.; Hansen, T.; Rutberg, J.; Bruzinski, P.R. Tetrahedron Lett. 1997, 38, 1741. Ge, M.; Corey, E.J. Tetrahedron Lett. 2006, 47, 2319.)

Method used

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  • Spiro bisimine and preparation method and application thereof
  • Spiro bisimine and preparation method and application thereof
  • Spiro bisimine and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Example 1: (R)-N, N'-[1-(2,6-dichlorophenyl)-methylene]-1,1'-spirodihydroindane-7,7'-diamine

[0024]

[0025] Add (R)-1,1'-spirodihydroindane-7,7'-diamine (800mg, 3.2 mmol), 2,6-dichlorobenzaldehyde (1.56g, 9.0mmol) and 9.6g Molecular sieve, replace the system with nitrogen atmosphere. Add freshly distilled toluene (60mL) and freshly distilled NEt to the system 3 (1.9 mL), stirred and reacted at 80°C for three days, filtered and washed the filter residue with dichloromethane (20 mL), combined the filtrates, and recrystallized the residue obtained after rotary evaporation and precipitation with ethanol to obtain a yellow solid with a yield of 60%. Melting point: 128-130°C. -21.0 (c0.5, CH 2 Cl 2 ). 1 H NMR (300MHz, CDCl 3 ): δ8.37(s, 2H), 7.14-6.90(m, 10H), 6.50-6.48(m, 2H), 3.03-2.89(m, 4H), 2.53-2.43(m, 2H), 2.20-2.14 (m, 2H). 13 C NMR (75MHz, CDCl 3 ): δ154.7, 148.6, 144.9, 142.1, 135.6, 131.5, 130.1, 128.8, 127.5, 122.2, 116.0, 60.5, 38.2, 31.2.

Embodiment 2

[0026] Example 2: (R)-N, N'-[1-(2,4-dichlorophenyl)-methylene]-1,1'-spirodihydroindane-7,7'-diamine

[0027]

[0028] The synthesis method is the same as in Example 1, with 2,4-dichlorobenzaldehyde replacing 2,6-dichlorobenzaldehyde. The product is a yellow solid with a yield of 56%. Melting point: 181-183°C. +287(c0.5, CH 2 Cl 2 ). 1 H NMR (300MHz, CDCl 3 ): δ8.38(s, 2H), 7.28-7.25(m, 2H), 7.14-7.13(m, 4H), 6.99-6.95(m, 2H), 6.77-6.66(m, 4H), 3.16-2.96 (m, 4H), 2.43-2.28 (m, 4H). 13 C NMR (75MHz, CDCl 3 ): δ152.9, 147.2, 144.3, 143.6, 136.8, 135.6, 132.2, 129.7, 129.1, 127.5, 127.2, 122.5, 115.1, 60.1, 38.0, 31.2.

Embodiment 3

[0029] Example 3: (R)-N, N'-[1-(2-chlorophenyl)-methylidene]-1,1'-spirodihydroindane-7,7'-diamine

[0030]

[0031] The synthetic method is the same as in Example 1, and 2,6-dichlorobenzaldehyde is replaced with 2-chlorobenzaldehyde. The product is a yellow solid with a yield of 94%. Melting point: 138-140°C. +181(c0.5, CH 2 Cl 2 ). 1 H NMR (300MHz, CDCl 3 ): δ 8.64(s, 2H), 7.38-7.20(m, 8H), 7.15-7.04(m, 4H), 6.85-6.82(m, 2H), 3.31-3.12(m, 4H), 2.65-2.42( m, 4H). 13 C NMR (75MHz, CDCl 3 ): δ 154.4, 147.7, 144.3, 143.5, 135.3, 133.8, 131.5, 129.4, 129.0, 127.6, 126.7, 122.4, 115.4, 60.3, 38.1, 31.4.

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Abstract

The invention relates to a spiro bisimine and a preparation method and application thereof. Spiro diamine is adopted as raw material to generate spiro bisimine. The spiro skeleton structure in the spiro bisimine has axial chirality, therefore, the class of compound has two optical isomers, namely, right spiro bisimine and left spiro bisimine; and the commensurable mixture of the two optical isomers become racemization spiro bisimine. The complex compound of the spiro bisimine and copper can be taken as a chiral catalyst which is used in asymmetric insertion reaction of carbene to silicon-hydrogen bond, and has very high activity and enantio selectivity (as high as 99.2 percent ee). The chemical formula of the spiro bisimine is as follows: n=0-3; and the values of R<1>, R<2>, R<3>, R<4>, R<5>, R<6>, R<7>, R<8>, R<9> and R<10> are defined as claim of right 1.

Description

technical field [0001] The invention relates to a spirocyclic bisimine, a preparation method and an application thereof. The spirocyclic bisimine is complexed with the copper precursor, and then ion exchanged to obtain copper / spirocyclic bisimine complexes containing different anions. The complex of spirobiimine and copper can be used as a chiral catalyst in the asymmetric insertion reaction of carbene to silicon-hydrogen bond, and has high activity and enantioselectivity (up to 99.2% ee). This is one of the most efficient catalysts for transition metal-catalyzed asymmetric carbene insertion reactions. Background technique [0002] Asymmetric catalytic synthesis is a hot spot in the field of organic synthetic chemistry research (Ohkuma, T.; Kitamura, M.; Noyori, R. Catalytic Asymmetric Synthesis, Wiley: New York, 2000.). The key to asymmetric catalytic synthesis is how to design and synthesize chiral catalysts with high enantioselectivity and catalytic activity. The desig...

Claims

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Application Information

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IPC IPC(8): C07C211/61C07C211/60C07D213/53C07F7/08B01J31/22
Inventor 伍新燕陈超张永振周其林
Owner EAST CHINA UNIV OF SCI & TECH
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