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Spirobi(dihydrobenzosilole) diphenol compound, and synthesis method and application thereof

A technology of spirobisdihydrobenzothiazole diphenols and compounds, which is applied in the field of spirobisdihydrobenzothiazole diphenols and can solve the problem of single ligands and the like

Active Publication Date: 2020-06-02
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

[0004] The technical problem to be solved by the present invention is to provide a kind of spirobisdihydrobenzothiazole diphenol compound, its preparation method and application

Method used

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  • Spirobi(dihydrobenzosilole) diphenol compound, and synthesis method and application thereof
  • Spirobi(dihydrobenzosilole) diphenol compound, and synthesis method and application thereof
  • Spirobi(dihydrobenzosilole) diphenol compound, and synthesis method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0392] Example 1: Synthesis of chiral diphenol compounds with spirobisdihydrobenzosilole skeleton

[0393]

[0394] step 1)

[0395] In a nitrogen atmosphere, methyltriphenylphosphine bromide (15.25g, 42.7mmol) and potassium tert-butoxide (6.0g, 53,4mmol) and 50mL tetrahydrofuran were mixed with a 200mL dry Schlenk bottle, and stirred at room temperature for 0.5h , the tetrahydrofuran solution dissolved in 1-(2-bromo-3-methoxyphenyl)ethanone (8.12g, 35.6mmol) was added dropwise to the previous step system, TLC detected that the reaction was complete, and quenched by dropping saturated ammonium chloride aqueous solution reaction, extracted three times with ethyl acetate, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, allowed to stand, and the desiccant was removed by suction filtration, and the filtrate was purified by column chromatography to obtain 2-bromo-1 -Methoxy-3-(prop-1-en-2-yl)benzene (7.07 g, yield: 88%).

[0396] step (2...

Embodiment 2

[0408] Embodiment 2: I-2

[0409]

[0410] Use (2S,4S)-2,4-bis(diphenylphosphonium)pentane to replace (2R,4R)-2,4-bis(diphenylphosphonium)pentane, with reference to the reaction conditions in Example 1 and The method of operation is prepared.

[0411] White solid, 96% yield, [a] D 24 =-4.23 (c=0.90, CHCl 3 ); 1 H NMR (400MHz, CDCl 3 )δ7.28(t, J=7.8Hz, 2H), 6.95(d, J=7.6Hz, 2H), 6.56(d, J=7.9Hz, 2H), 4.51(s, 2H), 3.60–3.42( m,2H),1.75(dd,J=15.1,8.1Hz,2H),1.38(d,J=7.0Hz,6H),0.94(dd,J=15.1,4.7Hz,2H); 13 C NMR (100MHz, CDCl 3 )δ161.58, 159.71, 132.73, 120.39, 117.88, 112.02, 38.65, 25.46, 20.44; HRMS (ESI-TOF) m / z Calcd for C 18 h 21 o 2 Si[M+H] + :297.1305,found:297.1304.

[0412] Use corresponding raw material, with reference to reaction condition and operation method in embodiment 1 or 2, prepare following compound:

Embodiment 3

[0413] Embodiment 3: I-3

[0414]

[0415] White solid, 92% yield, [a] D 25 =+3.5 (c=1.07, CHCl 3 ); 1 H NMR (400MHz, CDCl 3 )δ7.29–7.19(m,2H),6.91(d,J=7.5Hz,2H),6.53(d,J=7.9Hz,2H),4.59(s,2H),3.38–3.06(m,4H ),1.51–1.35(m,2H),1.31–1.13(m,2H); 13 C NMR (100MHz, CDCl 3)δ160.03, 156.69, 132.60, 121.38, 118.75, 111.83, 31.67, 9.40; HRMS (ESI-TOF) m / z Calcd for C 16 h 17 o 2 NaSi[M+Na] + :291.0812,found:291.0815.

[0416] Single crystal culture conditions: Dissolve 10 mg of the compound in 0.5 mL of dichloromethane in an 8 mL vial, add 4 mL of n-hexane, cover the bottle with a hole, and let it stand for 0.5-1 day. The crystal was subjected to single crystal diffraction test.

[0417] The crystals were subjected to X-ray diffraction detection, as attached figure 1 structure, consistent with the target structure.

[0418]

[0419]

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Abstract

The invention discloses a spirobi(dihydrobenzosilole) diphenol compound represented by formula I shown in the specification, and a synthesis method and an application thereof, and concretely providesa method for efficiently constructing the spirobi(dihydrobenzosilole) diphenol compound represented by formula I by using cheap and easily available initial raw materials. The method has the characteristics of simplicity and convenience in operation, easily available raw materials, mild reaction conditions, high yield, convenience in purification and the like. The spirobi(dihydrobenzosilole) diphenol compound of the formula I can be directly used as an organic catalyst, or can be used together with group III to group XIII metal salts to generate a metal complex or be used in an in-situ mixed manner to catalyze an asymmetric organic synthesis reaction; and the compound has the advantages of realization of excellent yield and stereospecific conversion under mild conditions, good substrate universality, and great expansion of the research process of asymmetric catalysis.

Description

technical field [0001] The invention relates to a spirobis-dihydrobenzothiazole diphenol compound, a synthesis method and an application thereof. Background technique [0002] Chirality is one of the most important properties in nature, and it is also an important symbol that distinguishes living matter from non-living matter. In the pharmaceutical industry, chirality is also directly related to the pharmacological action, clinical effect, side effects, drug effect and drug effect time of the drug. For example, in the 1960s, due to insufficient understanding of chirality, Thalidomide was used as a sedative for anti-pregnancy reactions in Europe, resulting in the emergence of many abnormal fetuses. Later studies have confirmed that (R)-Thalidomide really acts as a sedative, while (S)-Thalidomide has a strong teratogenic effect. Because of this, the development of methods for constructing optically homochiral compounds is crucial to the technological innovation and reserve o...

Claims

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Application Information

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IPC IPC(8): C07F7/08B01J31/22B01J31/30B01J31/02C07F7/10C07C29/38C07C33/30C07D209/42
CPCB01J31/0275B01J31/1608B01J31/186B01J31/30B01J2531/0241B01J2531/16B01J2531/824C07B2200/13C07C29/38C07D209/42C07F7/0812C07F7/0816C07C33/30
Inventor 王鹏常鑫马培龙
Owner SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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