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Spiro phosphine-oxazoline and preparation method and application thereof

A technology of oxazoline and spiro ring, applied in the field of new spiro phosphine-oxazoline and preparation, can solve the problems of reducing the scope of application of SIPHOX ligand substrates and high cost of SIPHOX ligand synthesis

Active Publication Date: 2009-10-28
ZHEJIANG JIUZHOU PHARM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, due to the use of optically pure aminoalcohol compounds as synthetic raw materials in the synthesis of ligands, the synthesis cost of SIPHOX ligands is relatively high; at the same time, due to the steric hindrance effect of the substituent on the 4-position of the oxazoline ring, certain Some substrates cannot coordinate close to metal atoms, which reduces the scope of application of SIPHOX ligands.

Method used

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  • Spiro phosphine-oxazoline and preparation method and application thereof
  • Spiro phosphine-oxazoline and preparation method and application thereof
  • Spiro phosphine-oxazoline and preparation method and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0040] Embodiment 1: (S a Preparation of )-N-hydroxyethyl-7'-bis(3,5-di-tert-butylphenyl)phosphino-1,1'-spirodihydroindene-7-carboxamide

[0041]

[0042] Weigh (S a )-7-bis(3,5-di-tert-butylphenyl)phosphino-7'-carboxy-1,1'-spirodihydroindane 1 (1.0g, 1.48mmol), aminoethanol (284mg, 4.65mmol ), 1-hydroxybenzotriazole (HOBt, 504mg, 3.29mmol) and dicyclohexylcarboimide (DCC, 881mg, 4.27mmol). Added redistilled tetrahydrofuran (THF, 80mL) under ice-water cooling, after the addition, the reaction was naturally raised to room temperature and stirred, and a large amount of white precipitates formed in the system. TLC followed the reaction until conversion was complete. Then add 5g of silica gel, rotary evaporation precipitation, dry column, with sherwood oil / ethyl acetate mixed solvent (v / v=1: 1) as eluent to carry out silica gel column chromatography, to obtain compound (S a )-N-Hydroxyethyl-7'-bis(3,5-di-tert-butylphenyl)phosphino-1,1'-spiroindane-7-carboxamide 2 (660 mg, 6...

Embodiment 2

[0045] Embodiment 2: (S a Preparation of )-7-(4,5-dihydrooxazol-2-yl)-7'-bis(3,5-di-tert-butylphenyl)phosphino-1,1'-spiroindene

[0046]

[0047] In a 100mL Schlenk reaction flask equipped with electromagnetic stirring, weigh (S a )-N-hydroxyethyl-7'-bis(3,5-di-tert-butylphenyl)phosphino-1,1'-spirodihydroindane-7-carboxamide 2 (660mg, 0.92mmol) and 4 - Dimethylaminopyridine (DMAP, 5mg, 0.041mmol), the vacuum line was replaced with a nitrogen atmosphere, and 60mL of degassed dichloromethane was added and stirred evenly. Under cooling in an ice-water bath, 0.28 mL of triethylamine and methanesulfonyl chloride (MsCl, 105 μL, 1.36 mmol) were sequentially added, kept stirring for 30 minutes, and then 1.20 mL of triethylamine was added, and allowed to rise to room temperature and stirred overnight. TLC followed the reaction until conversion was complete. Add 5g of silica gel to the system to quench the reaction, and then directly dry-load the column after vacuum precipitation,...

Embodiment 3

[0050] Embodiment 3: [(S a - Preparation of DTB-SIPHOX)Ir(COD)]BARF

[0051]

[0052] Weigh the ligand (S a )-7-(4,5-dihydrooxazol-2-yl)-7'-bis(3,5-di-tert-butylphenyl)phosphino-1,1'-spirodihydroindene 3 (60mg , 0.085mmol), [Ir(COD)Cl] 2 (32mg, 0.047mmol) and NaBARF (100mg, 0.107mmol) in a 15mL Schlenk reaction flask, after taking it out, add freshly distilled dichloromethane (2mL) with a syringe, heat and stir in a water bath at 45°C for 1 hour, and monitor by thin-layer chromatography For the reaction situation, stop heating when the ligands are completely complexed, and allow the system to cool down to room temperature naturally. After rotary evaporation precipitation, residue column chromatography can be obtained [(S a -DTB-SIPHOX)Ir(COD)]BARF4 (132 mg, 82%). The product was an orange foamy solid. Mp 196°C; [α] D 21 +122.6(c 0.5, CH 2 Cl 2 ); 1 H NMR (300MHz, CDCl 3 )δ7.65 (brs, 9H, Ar-H), 7.50-7.35 (m, 8H, Ar-H), 7.27-7.24 (m, 1H, Ar-H), 7.18-7.07 (m, 4H, A...

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Abstract

The invention belongs to spirophosphine-oxazoline and a preparation method and an application thereof, in particular to novel spirophosphine-oxazoline and a preparation method of iridium complex thereof. The novel spirophosphine-oxazoline is synthesized through two reactions by using substitutional 7-diarylphosphino-7'-carboxyl-1, 1'-spirobiindane as starting raw materials. Complexation and ion exchange are performed for the novel spirophosphine-oxazoline and iridium precursor, so as to obtain iridium / spirophosphine-oxazoline complex compound containing different anions. The invention overcomes the defects of the prior art, synthesizes the novel spirophosphine-oxazoline without substitutional group on oxazoline 4- position by using cheap aminoethanol as raw materials, can catalyze asymmetric hydrogenation reaction of Alpha-substituting acrylic acid, expresses higher activity and enantioselectivity and has higher research value and industrial prospect.

Description

technical field [0001] The invention relates to a novel spirocyclic phosphine-oxazoline, a preparation method and application thereof. Specifically, the novel spirophosphine-oxane of the present invention is synthesized through two-step reaction with substituted 7-diarylphosphino-7'-carboxy-1,1'-spirodihydroindene as starting material. oxazoline. The novel spirophosphine-oxazoline is complexed with the iridium precursor, and then ion-exchanged to obtain iridium / spirophosphine-oxazoline complexes containing different anions. The iridium complex of the novel spirocyclic phosphine-oxazoline can catalyze the asymmetric hydrogenation reaction of α-substituted acrylic acid, showing high activity and enantioselectivity. Background technique [0002] Asymmetric catalytic synthesis is a hotspot 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 ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/653C07F15/00C07C51/36B01J31/24B01J31/28
CPCC07F15/0033C07F15/0046C07B2200/07C07F9/653C07C51/36B01J31/189B01J2231/645B01J2531/827C07C59/68C07C57/30
Inventor 周其林朱守非李珅王立新宋颂
Owner ZHEJIANG JIUZHOU PHARM CO LTD
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