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Spiroindane skeleton chiral quaternary ammonium salt as well as preparation method and application thereof

A technology of spiroindane and quaternary ammonium salt, which is applied in the field of chiral quaternary ammonium salt of spirodihydroindane skeleton and its preparation, which can solve the problems of limited range of substrates in asymmetric catalytic reactions and achieve the effect of enriching types

Pending Publication Date: 2022-04-01
TIANJIN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[(a) Ooi, T.; Maruoka, K. Aldrichimica Acta 2007, 40, 77; (b) Hashimoto, T.; Maruoka, K. Chem. Rev. 2007, 107, 5656] However, due to the asymmetric catalytic reaction specificity, each type of catalyst is often only effective for one or a few types of reaction substrates, and the range of substrates for many asymmetric catalytic reactions is very limited

Method used

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  • Spiroindane skeleton chiral quaternary ammonium salt as well as preparation method and application thereof
  • Spiroindane skeleton chiral quaternary ammonium salt as well as preparation method and application thereof
  • Spiroindane skeleton chiral quaternary ammonium salt as well as preparation method and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0029] Example 1: (R)-12,12-diethyl-1,10-diphenyl-4,5,6,7,12,13-hexahydro-11H-diindeno[7,1-cd : Preparation of 1',7'-ef]azocetine bromide[(R)-Va]

[0030]

[0031] Step 1, under nitrogen atmosphere, add (R)-6,6'-diiodo-1,1'-spirodihydroindane-7,7'-dicarboxylic acid dimethyl ester [(R)-I, 2mmol] , phenylboronic acid (8mmol), bis(triphenylphosphine)palladium chloride (0.5mmol), potassium carbonate aqueous solution (1.5mol / L, 6mL), methanol (4mL) and tetrahydrofuran (25mL) were sequentially added to a 100mL reaction flask , heated to 85°C and stirred for 24 hours. After the reaction was completed, most of the solvent was evaporated, the residue was diluted with water (20mL), transferred to a separatory funnel, extracted three times with ethyl acetate (50mL), the organic phases were combined, washed once with saturated brine (50mL), added Anhydrous sodium sulfate was allowed to stand for a while. The desiccant was filtered off, most of the solvent was removed by rotary evapo...

Embodiment 2

[0035] Example 2: 1,10-diphenyl-4,5,6,7-tetrahydro-11H,13H-spiro[bisindeno[7,1-cd:1',7'-ef]azocine Preparation of cyclo-12,4'-morpholine] bromide [(R)-Vb]

[0036]

[0037] Step 1, under nitrogen atmosphere, add (R)-6,6'-diiodo-1,1'-spirodihydroindane-7,7'-dicarboxylic acid dimethyl ester [(R)-I, 2mmol] , phenylboronic acid (8mmol), bis(triphenylphosphine)palladium chloride (0.5mmol), potassium carbonate aqueous solution (1.5mol / L, 6mL), methanol (4mL) and tetrahydrofuran (25mL) were sequentially added to a 100mL reaction flask , heated to 85°C and stirred for 24 hours. After the reaction was completed, most of the solvent was evaporated, the residue was diluted with water (20mL), transferred to a separatory funnel, extracted three times with ethyl acetate (50mL), the organic phases were combined, washed once with saturated brine (50mL), added Anhydrous sodium sulfate was allowed to stand for a while. The desiccant was filtered off, most of the solvent was removed by rot...

Embodiment 3

[0041] Example 3: (R)-12,12-diethyl-1,10-bis(4-methylphenyl)-4,5,6,7,12,13-hexahydro-11H-diindeno Preparation of [7,1-cd:1',7'-ef]azococtyl bromide [(R)-Vc]

[0042]

[0043] Step 1, under nitrogen atmosphere, add (R)-6,6'-diiodo-1,1'-spirodihydroindane-7,7'-dicarboxylic acid dimethyl ester [(R)-I, 2mmol] , 4-methylphenylboronic acid (8mmol), bis(triphenylphosphine)palladium chloride (0.5mmol), potassium carbonate aqueous solution (1.5mol / L, 6mL), methanol (4mL) and tetrahydrofuran (25mL) were added to In a 100mL reaction flask, heat up to 90°C and stir for 24 hours. After the reaction was completed, most of the solvent was evaporated, the residue was diluted with water (20mL), transferred to a separatory funnel, extracted three times with ethyl acetate (50mL), the organic phases were combined, washed once with saturated brine (50mL), added Anhydrous sodium sulfate was allowed to stand for a while. The desiccant was filtered off, most of the solvent was removed by rotary...

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Abstract

The invention relates to spirobiindane skeleton chiral quaternary ammonium salt as well as a preparation method and application thereof. The preparation method comprises the following steps: under the action of bis (triphenylphosphine) palladium chloride and potassium carbonate, enabling optically active 6, 6 '-diiodo-1, 1'-spirobiindane-7, 7 '-dimethyl diformate to react with arylboronic acid to generate 6, 6'-disubstituted-1, 1 '-spirobiindane-7, 7'-dimethyl diformate; the preparation method comprises the following steps: reacting 6, 6 '-disubstituted-1, 1'-spirobiindane-7, 7 '-dimethanol with diisobutylaluminium hydride to generate 6, 6'-disubstituted-1, 1 '- The preparation method comprises the following steps: reacting 7, 7 '-disubstituted-7, 7'-bis (bromomethyl)-1, 1 '-spirobiindene with phosphorus tribromide to generate 6, 6'-disubstituted-7, 7 '-bis (bromomethyl)- And reacting with secondary amine under the action of potassium carbonate to generate corresponding chiral quaternary ammonium salt. The spirobiindane skeleton chiral quaternary ammonium salt can be used for catalyzing an asymmetric alkylation reaction of diphenylmethylene glycine tert-butyl ester and pentafluorobenzyl bromide, the highest yield of the obtained product can reach 98%, and the highest enantioselectivity can reach 95% ee.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis chemistry, and specifically relates to a chiral quaternary ammonium salt with a spirodihydroindane skeleton, a preparation method and an application. Background technique [0002] As an important branch in the field of asymmetric catalysis, asymmetric phase transfer catalysis usually has the advantages of mild conditions, simple operation, environmental friendliness, and easy scale-up production, which has attracted the attention of both academia and industry. [(a) Ooi, T.; Maruoka, K.Angew.Chem.Int.Ed.2007, 46, 4222; (b) Shirakawa, S.; Maruoka, K.Angew.Chem.Int.Ed.2013, 52 , 4312; (c) Tan, J.; Yasuda, N. Org. Process Res. Dev. 2015, 19, 1731; (d) D.; Modrocká, V.; M.; R. ChemSusChem2020, 13, 2828] In many asymmetric phase transfer catalytic reactions, chiral quaternary ammonium salts are the most widely used catalysts. In 1999, Maruoka designed and synthesized a chiral quaternary...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D225/04C07D498/10C07D471/10B01J31/02C07C251/24C07C249/02
Inventor 李珅荣萌郁封芳芳马军安
Owner TIANJIN UNIV
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