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Chiral bridged aryloxyalkyloxy scandium chloride, and preparation method and application thereof

An aryloxyalkoxy scandium and chloride technology, which is applied in the field of asymmetric catalysis, can solve problems that have not yet been seen, and achieves the effects of a wide range of substrate adaptation, a clear compound structure, and mild reaction conditions.

Inactive Publication Date: 2014-07-30
ZHANGJIAGANG INST OF IND TECH SOOCHOW UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0018] So far, there is no report on the preparation of chiral α-hydroxyphosphonate by using chiral bridged aryloxyalkoxy rare earth metal compounds as catalysts to catalyze the asymmetric hydrophosphine reaction of α, β-unsaturated ketones

Method used

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  • Chiral bridged aryloxyalkyloxy scandium chloride, and preparation method and application thereof
  • Chiral bridged aryloxyalkyloxy scandium chloride, and preparation method and application thereof
  • Chiral bridged aryloxyalkyloxy scandium chloride, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] Example 1: Preparation of LScCl(THF)

[0050] 1) Before preparing the chiral bridged aryloxyalkoxy scandium compound, first prepare LH 2 , its preparation method is as follows:

[0051] Add 3 ml (30 mmol) of formaldehyde solution into a two-neck flask with stirring bar, add methanol to dissolve, then add (S)-α, 5.07 g (20 mmol) of α-diphenylprolinol, and stir the reaction After half an hour, 4.12 g (20 mmol) of 2,4-di-tert-butylphenol was added. After reacting at 60°C for 24 hours, a large amount of white solid precipitated out. Suction filtration, washing the filter cake with methanol, and drying to obtain the compound LH 2 , yield 80%. NMR data: 1 H NMR (400MHz, CDCl 3 ): 7.60(dd, 4H), 7.32(m, 4H), 7.21(t, 1H), 7.18-7.08(m, 2H), 6.70(s, 1H), 3.99(m, 1H), 3.41(dd, 2H), 2.90(s, 1H), 2.43(m, 1H), 2.15-2.01(m, 1H), 1.96-1.83(m, 1H), 1.70(m, 2H), 1.39(s, 9H), 1.24 (s,9H).

[0052] 2) Preparation of LScCl(THF)

[0053] Add LH to a reaction flask that strictly remo...

Embodiment 2

[0054] Example 2: Using the LScCl (THF) prepared above to catalyze the asymmetric hydrophosphine reaction of α, β-unsaturated ketones:

[0055] In the reaction flask that has been treated with dehydration and deoxygenation, add 0.0625 g (0.3 mmol) of chalcone and 0.019 g (0.03 mmol) of chiral bridged aryloxyalkoxy scandium chloride under the protection of argon, and add 2.0 ml of tetrahydrofuran was stirred in a constant temperature bath with a set temperature of 10°C for 5 minutes, and then 0.058 ml of diethyl phosphinate was added. After continuing the reaction at 10° C. for 4 h, the reaction was terminated with deionized water.

[0056] The product was separated on a silica gel column, and finally eluted with an eluent of ethyl acetate:petroleum ether=1:1 to obtain 45.72 mg of α-hydroxyphosphonate with a yield of 44%. Enantioselectivity was determined by chiral HPLC, Daicel Chiralpak AS-H column, eluent i-PrOH / hexane (10 / 90), flow rate 1.0mL / min, ee value 37%.

Embodiment 3

[0057] Example 3: Using the LScCl (THF) prepared above to catalyze the asymmetric hydrophosphine reaction of α, β-unsaturated ketones:

[0058] In the reaction flask that has been treated with dehydration and deoxygenation, add 0.0625 g (0.3 mmol) of chalcone and 0.019 g (0.03 mmol) of chiral bridged aryloxyalkoxy scandium chloride under the protection of argon, and add 2.0 ml of toluene was stirred in a constant temperature bath with a set temperature of 10° C. for 5 minutes, and then 0.058 ml of diethyl phosphinate was added. After continuing the reaction at 10° C. for 4 h, the reaction was terminated with deionized water.

[0059]The product was separated on a silica gel column, and finally washed with an eluent of ethyl acetate:petroleum ether=1:1 to obtain 56.11 mg of α-hydroxyphosphonate with a yield of 54%. Enantioselectivity was determined by chiral HPLC, Daicel Chiralpak AS-H column, eluent i-PrOH / hexane (10 / 90), flow rate 1.0mL / min, ee value 42%.

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Abstract

The invention discloses a chiral bridged aryloxyalkyloxy scandium chloride. The chiral bridged aryloxyalkyloxy scandium chloride is characterized in that the chiral bridged aryloxyalkyloxy scandium chloride has a general formula of LScCl(THF), and has a chemical structural formula shown in the specification, and L is (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)-phenolate. The above compound has the advantages of simple synthesis, clear structure and high yield. The invention also provides a preparation method of the compound, and an application method of the compound in the catalysis of the asymmetric hydrogen phosphorization reaction of alpha, beta-unsaturated ketone as a catalyst. The application method has the advantages of mild conditions, high selectivity, good antipodal selectivity and wide substrate adaptation range.

Description

technical field [0001] The invention relates to the field of asymmetric catalysis, in particular to a chiral bridged aryloxy alkoxy scandium chloride, a preparation method thereof and an application in asymmetric hydrogen phosphine reaction. Background technique [0002] Optically pure phosphine compounds have a wide range of applications, and it is of great significance to develop effective methods for synthesizing optically pure phosphine compounds. The most direct, efficient, and atom-economical way to form chiral P-C bonds is through the asymmetric addition of P-H bonds to C=C double bonds. At present, there are many kinds of catalysts that can catalyze this kind of reaction, mainly including organic small molecule catalytic system and metal complex catalytic system. [0003] Reports on small organic molecule systems: [0004] (1) In 2007, Terada et al. used an axial chiral guanidine compound derived from binaphthol for the first time to catalyze the 1,4-addition of di...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/00B01J31/22C07F9/40
Inventor 姚英明檀玉芳
Owner ZHANGJIAGANG INST OF IND TECH SOOCHOW UNIV
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