Chiral cyclopropane alkamine ligand compound, and preparation and application thereof

A technology for cyclopropaneamino and ligand compounds, which is applied to chiral cyclopropaneamino alcohol ligand compounds and the fields of preparation and application thereof, can solve problems such as the limitation of ligand development, and achieve the effects of high stereoselectivity and mild reaction conditions

Inactive Publication Date: 2011-06-15
CHINA AGRI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

This has greatly restricted the development of ligands

Method used

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  • Chiral cyclopropane alkamine ligand compound, and preparation and application thereof
  • Chiral cyclopropane alkamine ligand compound, and preparation and application thereof
  • Chiral cyclopropane alkamine ligand compound, and preparation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1: Preparation of (1R, 3S)-3-formyl-2,2-dimethylcyclopropanecarboxylic acid methyl ester

[0031] First add 250mL of methanol into a 500mL four-neck flask, then add 42.6g (300mmol) of carvalolactone, 10g (58mmol) of p-toluenesulfonic acid, stir rapidly and raise the temperature to reflux for 5h. Heating was stopped, 10 g (120 mmol) of sodium acetate was added, and the methanol was spun off under reduced pressure. 250 mL of n-hexane was added to the residue, the organic phase was washed three times with 100 mL of water, and then the organic phase was spun off. Add 200 mL of 0.5% oxalic acid aqueous solution to the residue, stir rapidly at room temperature for 10 h, extract three times with 100 mL of ether, combine the organic phases, anhydrous Na 2 SO 4 Dried and spin-dried to obtain 31 g of light yellow oil, which was directly used in the next reaction without purification.

Embodiment 2

[0032] Embodiment 2: Preparation of (1R, 3S)-3-(prolinol-1-methyl)-2,2-dimethylcyclopropanecarboxylic acid methyl ester

[0033] First add 80mL of methanol to a 250mL four-necked bottle, add 8.08g (80mmol) (or D-prolinol), slowly add 1mL (20mmol) of concentrated sulfuric acid dropwise, and then add 3.12g (40mmol) of caronaldehyde ester and 2g (32mmol) NaBH 3 CN. The above solution was stirred rapidly at room temperature for 16 hours, then concentrated hydrochloric acid was added dropwise to make the pH10, extract three times with 15 mL of diethyl ether, combine the organic phases, anhydrous MgSO 4 Dry and purify.

[0034] 5a: Column chromatography: anhydrous diethyl ether, a light yellow oily liquid was obtained with a yield of 78%. [α] D 20 =-49.1 (c=1.46, CHCl 3 ); IR (neat) 3427, 2952, 2875, 1727, 1438, 1385, 1277, 1178, 1140, 1091, 1045cm -1 ; 1 H NMR (300MHz, CDCl 3 ): δ3.69-3.62(m, 4H), 3.39-3.35(m, 1H), 3.20-3.07(m, 2H), 3.86(br, 1H), 2.66-2.59(m, 2H), 2.29-2.2...

Embodiment 3

[0036] Example 3: Preparation of (1R, 3S)-3-(prolinol-1-methyl)-2,2-dimethylcyclopropanediphenylmethanol

[0037] Under the protection of nitrogen, first add 1.2g (5mmol) prolinol cyclopropane ester, then add anhydrous THF 5mL, slowly add 10mL PhMgCl (2mol / L) dropwise under ice bath, after the dropwise addition is completed, rise to room temperature and continue the reaction for 12h. After the reaction was complete, 5 mL of saturated NH 4 Cl, extracted three times with ether 10mL and combined organic phase, anhydrous Na 2 SO 4 After drying, the solvent was removed to obtain a white solid, which was purified by recrystallization.

[0038] 6a: white solid, yield 82%, mp 89-91 °C, [α] D 20 =+37.1 (c=2.48, CHCl 3 ); IR (KBr) 3413, 3057, 3010, 2931, 2873, 2818, 1600, 1491, 1447, 1413, 1374, 1304, 1077, 1028, 752, 702cm -1 ; 1 H NMR (300MHz, CDCl 3 ): δ7.58-7.49(m, 4H), 7.32-7.24(m, 4H), 7.18-7.15(m, 2H), 5.50(br, 1H), 3.28(d, J=4Hz, 1H), 3.07 -2.93(m, 2H), 2.80-2.74(m, 2H)...

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PUM

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Abstract

The invention discloses a chiral cyclopropane alkamine ligand compound, and preparation and application thereof and belongs to the technical field of chiral ligand compounds. The chiral cyclopropane alkamine ligand compound has the structural general formula shown as the specifications. The chiral cyclopropane alkamine ligand compound can be prepared from carane aldehyde acid lactone through four-step reaction. The chiral cyclopropane alkamine ligand compound can be applied to asymmetric addition of alkyne at the tail end to aldehyde. The ligand compound reacts with a metal reagent to preparea zinc, nickel or copper complex catalyst used for catalyzing an asymmetric alkynylation reaction. Compared with the technology reported by documents, the invention has the advantages that: the asymmetric alkynylation reaction is catalyzed by the ligand compound, so the reaction condition is mild, other auxiliary reagents are not required, stereoselectivity is high, and a chiral ligand is derivedfrom cheap pyrethrin.

Description

technical field [0001] The invention belongs to the technical field of chiral ligand compounds, in particular to a chiral cyclopropane aminoalcohol ligand compound and its preparation and application. Background technique [0002] Chiral amino alcohols are a very important class of intermediates in organic synthesis and have wide applications in the fields of medicine, pesticides and materials science. In recent years, chiral aminoalcohol ligands with different structures have emerged, and chiral aminoalcohol metal complexes have attracted extensive attention due to their good catalytic effects in various asymmetric reactions. [0003] With the development of the pharmaceutical industry and the rise of chiral technology, it is of great significance to find a chiral ligand compound that is easy to prepare and has good catalytic performance for asymmetric synthesis research and industrial application. The current development of chiral ligands mainly focuses on using natural p...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/18B01J31/22C07B53/00C07B41/02C07C33/28C07C33/48C07C33/38C07C33/30C07C29/42C07C205/19C07C201/12C07C43/23C07C41/30C07F7/08C07C69/003C07C67/31
Inventor 钟江春李志愿郑冰毛建友郭红超王敏
Owner CHINA AGRI UNIV
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