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Phosphine compound of possessing plane chirality cyclophane alkyl, synthetic method, and appliction

A phosphine compound and compound technology are applied in the field of phosphine compounds and synthesis of cyclic aryl alkanes, and can solve the problems of difficult preparation, complex structure, easy oxidation and the like of planar chiral cyclo alkane compounds

Inactive Publication Date: 2007-07-25
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Some of these compounds have achieved good results in asymmetric synthesis as ligands or chiral auxiliary agents, but the derivatization of cycloaryl alkanes is difficult, and the preparation of planar chiral cycloaryl alkanes is even more difficult.
Chiral monophosphine is widely used in asymmetric synthesis, but it also has the characteristics of difficult preparation, complex structure and easy oxidation.

Method used

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  • Phosphine compound of possessing plane chirality cyclophane alkyl, synthetic method, and appliction
  • Phosphine compound of possessing plane chirality cyclophane alkyl, synthetic method, and appliction
  • Phosphine compound of possessing plane chirality cyclophane alkyl, synthetic method, and appliction

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Experimental program
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Effect test

Embodiment 1

[0024] Embodiment 1: Synthesis of planar chiral cycloaryl alkane monophosphine compound

[0025] At 0°C, add (3.444g, 12mmol) 4-bromo[2.2]p-cycloarane to the reaction flask, dissolve it in 150mL of ether, add butyllithium, stir for 1 hour, then add dihydrocarbylphosphine chloride, dihydrocarbyloxy Phosphorus chloride (take diphenylphosphine chloride as an example) (3.5ml, 18mmol), rise to room temperature and react for 8 hours, add 10mL methanol to quench, remove solvent under reduced pressure, silica gel column chromatography (petroleum ether: ethyl acetate = 15 : 1), to obtain the corresponding racemic cycloaryl alkane monophosphine compound H1a 3.669g, yield: 78%. Racemic H1a (0.392g, 1mmol) reacted with cyclopalladium A (0.339g, 0.5mmol) in 10mL of methanol for 0.5 hours, and was separated by silica gel column chromatography (petroleum ether: ethyl acetate = 3: 1) to obtain two non-pairs Enantiomers, reacting them with a dissociation reagent (0.5 mmol recommended sodium p...

Embodiment 2

[0068] Example 2: Synthesis of planar chiral ring aralkoxa monophosphine compound

[0069] With reference to literature (Cram, D.J.; Day, A.C.J.Org Chem.1966,31,1227), in a 250ml three-necked flask, add 4-bromo[2.2]paracyclic arane (3.444g, 12.0mmol), diethyl ether (150ml) , cooled to 0°C, added butyllithium (15ml, 24mmol), stirred at room temperature for 20 minutes, a light yellow solid precipitated, cooled to 0°C again, added freshly distilled trimethyl borate (2.7ml, 24mmol), stirred at room temperature for 1 After one hour, add 0.5M aqueous sodium hydroxide solution (6ml, 3mmol), 30% hydrogen peroxide aqueous solution (4.5ml, 45mmol), heat up to 40°C for 3 hours, cool to room temperature, add 30ml of water, 100ml of dichloromethane, and separate , the solvent was removed under reduced pressure, and purified by column chromatography (dichloromethane) to obtain the known compound 4-hydroxy[2.2]paracyclophane.

[0070] Add 4-hydroxy[2.2]p-cycloarane (202mg, 0.90mmol), toluen...

Embodiment 3

[0083] Embodiment 3: Application in asymmetric allyl amination reaction

[0084] For general operation, take 2-(acetoxy-p-nitrobenzyl)methyl acrylate as an example. Under the protection of argon, the raw material (0.5mmol), phthalimide (1.0mmol) and chiral catalyst (0.01mmol) were dissolved in 2ml of tetrahydrofuran, followed by spotting the reaction after completion of the reaction, and directly separated by silica gel column chromatography to obtain product. If (R)-H2 is used as a catalyst, the yield is 95%, ee(%): 70%.

[0085] 1 H NMR (300MHz, CDCl 3 )δ8.21(d, J=8.9Hz, 2H), 7.87-7.75(m, 4H), 7.61(d, J=9.0Hz, 2H), 6.63(s, 1H), 6.52(s, 1H), 5.66 (s, 1H), 3.72 (s, 3H); EIMS m / z (relative intensity) (%): 367 (M + ,<1), 147(51), 76(100).

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Abstract

This invention discloses a method for synthesizing planar chiral cycloaralkyl phosphine compound and its application. The chirality of the compound is derived from the planar chirality of cycloaralkyl framework. The method comprises: deriving from [2.2] dicycloaralkyl to obtain the compound, performing chiral resolution with chiral annulate Pd, separating the diastereoisomers by column chromatography to obtain planar chiral cycloaralkyl phosphine compound, and recovering annulate Pd. The compound, when used as catalyst in allyl amination and alkylation, has high reactivity and high antipode selectivity. Besides, the compound can be used as a ligand in asymmetric catalytic hydrogenation and aldehyde allylation. The compound has such advantages as high stability and simple synthesis.

Description

technical field [0001] The present invention relates to a kind of chiral compound, synthesis method and application, that is, a phosphine compound with planar chiral ring aromatic alkanes, synthesis method and application. Background technique [0002] Planar chiral [2.2] paracyclic alkane compounds are a very important class of planar chiral compounds with many distinctive characteristics. Hou Xuelong et al. have reported a planar chiral [2.2] paracyclic alkane oxazophosphine Ligand, synthesis method (ZL02136741.8). Some of these compounds have achieved good results in asymmetric synthesis as ligands or chiral auxiliary agents, but the derivatization of cycloarkanes is difficult, and the preparation of planar chiral cycloarkanes is even more difficult. Chiral monophosphine is widely used in asymmetric synthesis, but it also has the characteristics of difficult preparation, complex structure and easy oxidation. Therefore, looking for catalysts with relatively simple struct...

Claims

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Application Information

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IPC IPC(8): C07F9/50C07F9/28B01J31/24B01J31/28C07B53/00
Inventor 侯雪龙张唐志戴立信
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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