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Chiral spiro aminophosphine ligand compound and synthesis method as well as application thereof

A spiro-cyclic aminophosphine and spiro-amino-based technology, which is applied in the field of synthesis of chiral phosphine compounds, can solve problems such as unsatisfactory results and limited types, and achieve the effect of excellent reactivity

Inactive Publication Date: 2010-03-17
NANKAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the types of chiral aminophosphine ligands currently developed are still very limited, and the types of ligand skeletons are limited to binaphthyl skeletons, ferrocene skeletons, and simple aminoalcohol skeletons.
The chiral catalysts formed by their coordination with transition metals, such as complexes with ruthenium, have not achieved satisfactory results in the asymmetric catalytic hydrogenation of simple ketones, etc.

Method used

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  • Chiral spiro aminophosphine ligand compound and synthesis method as well as application thereof
  • Chiral spiro aminophosphine ligand compound and synthesis method as well as application thereof
  • Chiral spiro aminophosphine ligand compound and synthesis method as well as application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Synthesis of (R)-7-diphenylphosphino-7'-amino-1,1'-spiroindane (Ia-1)

[0035]

[0036] Under the protection of nitrogen, add 48mL of anhydrous chloroform into a 100mL two-neck bottle containing 0.50g (R)-II-1, stir well, and then add 1.6mL of concentrated sulfuric acid at one time. After heating the oil bath to 40-45°C, add 0.33g of sodium azide in batches. After adding sodium azide, reflux the oil bath and stir for four hours; remove the oil bath, cool to 0°C with ice water, add 100 mL of water to dilute the reaction, and adjust the pH value to slightly alkaline with sodium hydroxide solution; chloroform extraction, anhydrous Magnesium sulfate was dried; the magnesium sulfate was removed by filtration, and after drying, precipitation and silica gel column chromatography (ethyl acetate / petroleum ether=1 / 10) gave 0.46 g of white solid, yield 98%.

[0037] M.p.116-118°C; [α] D 20 +212(c 0.39, CH 2 Cl 2 ); 1 H NMR (300MHz, CDCl 3 )δ2.12-2.17 (m, 1H, CH 2 ), 2.2...

Embodiment 2

[0039] Synthesis of (R)-7-bis(p-methylphenyl)phosphino-7'-amino-1,1'-spirodihydroindane (Ia-2):

[0040]

[0041] Refer to Example 1 for specific operation, white solid, yield 80%.

[0042] M.p.108-110°C; [α] D 20 +184(c0.52, CH 2 Cl 2 ); 1 H NMR (300MHz, CDCl 3 )δ2.11-2.36 (m, 4H, CH 2 ), 2.27 (d, 6H, CH 3 ), 2.77(s, 2H, NH 2 ), 2.93-3.02 (m, 4H, CH 2 ), 6.06(d, 1H, Ar-H), 6.68(d, 1H, Ar-H), 6.87-7.23(m, 12H, Ar-H); 31 P NMR (121MHz, CDCl 3 )δ-23.80(s); 13 C NMR (75MHz, CDCl 3 )δ21.2, 21.3, 30.9, 31.2, 36.3, 39.3, 39.3, 61.5, 61.5, 114.2, 115.0, 125.8, 127.4, 128.1, 128.7, 128.9, 128.9, 133.1, 133.3, 134.0, 1364.2, 134.2, , 138.3, 142.5, 142.6, 144.3, 144.4, 144.7, 144.7, 152.8, 153.1, 162.3; HRMS (ESI) calcd for [C 31 h 30 NP+H] + : 448.2189; Found 448.2195.

Embodiment 3

[0044] Synthesis of (R)-7-bis(p-methoxyphenyl)phosphino-7'-amino-1,1'-spirodihydroindene (Ia-3)

[0045]

[0046] Refer to Example 1 for specific operation, white solid, yield 80%.

[0047] M.p.142-144°C; [α] D 20 +178(c 0.40, CH 2 Cl 2 ); 1 H NMR (300MHz, CDCl 3 )δ2.11-2.16 (m, 1H, CH 2 ), 2.21-2.36 (m, 3H, CH 2 ), 2.77(s, 2H, NH 2), 2.93-3.02 (m, 4H, CH 2 ), 3.76 (d, 6H, OCH 3 ), 6.07(d, 1H, Ar-H), 6.69-7.24(m, 12H, Ar-H); 31 P NMR (121MHz, CDCl 3 )δ-25.09(s); 13 C NMR (75MHz, CDCl 3 )δ30.9, 31.2, 36.3, 39.0, 39.1, 55.1, 55.2, 61.5, 61.5, 113.3, 113.7, 113.8, 113.9, 114.1, 115.0, 125.7, 127.4, 128.0, 130.0, 130.1, 133.8, 134.8, 134.5, , 135.6, 142.6, 144.3, 144.4, 144.7, 144.7, 152.5, 152.8, 159.6, 160.1; HRMS (ESI) calcd for [C 31 h 30 NO 2 P+H] + : 480.2087; Found 480.2095.

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Abstract

The invention relates to a chiral spiro aminophosphine ligand compound and a synthesis method as well as an application thereof. The chiral spiro aminophosphine compound contains a compound with a structure shown in I, or a racemic body or an optical isomer thereof, or a catalyzed acceptable salt thereof, wherein the main structure characteristic is with a chiral spirobiindane matrix. The chiral spiro aminophosphine compound can be synthesized by taking 7-diaryl / phosphito-7'-carboxy-1, 1'-spirobiindane or substituted 7-diaryl / phosphito-7'-carboxy-1, 1'-spirobiindane as chiral starting materials, which has optical activity and spiro matrix. The chiral spiro aminophosphine compound can be used as a chiral ligand for an asymmetrically catalyzed hydrogenation of an iridium catalyzed carboxy compound and achieves high yield and enantioselectivity (97%ee). The reactive activity is also high and the consumption of the catalyst can be reduced to 0.01% molar.

Description

technical field [0001] The invention relates to the synthesis of chiral phosphine compounds, in particular to a chiral spiro-aminophosphine ligand compound with a novel structure, a synthesis method and an application thereof. The chiral spiro-aminophosphine compound can be used as a chiral ligand in organic asymmetric reactions, specifically, it can be used in the asymmetric hydrogenation reaction of carbonyl compounds to prepare optically active compounds. Background technique [0002] Chiral aminophosphine ligand (Aminophosphine) is one of the very important chiral ligands. The complexes formed by their coordination with transition metals can be used to catalyze many asymmetric catalytic reactions, and give good reactivity and enantioselectivity (Amoroso, D.; Graham, T.W.; Guo, R.; Tsang, C.-W.; Abdur-Rashid, K. Aldrich. Chimica. Acta. 2008, 41, 15). For example, Morris et al. from the University of Toronto reported a series of NH-containing 2 Coordinating groups of am...

Claims

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Application Information

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IPC IPC(8): C07F9/50C07B53/00B01J31/24C07C29/145C07C33/22C07C33/20C07C33/18C07C33/34C07C33/46C07C33/24C07C35/36C07C35/32C07C31/125C07C31/135C07C33/30C07C35/21C07C35/17C07C35/50C07C33/14C07C41/26C07C43/23C07C43/315C07C41/50C07D333/16C07D307/42C07D211/86
Inventor 周其林谢建华谢剑波王立新
Owner NANKAI UNIV
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