Unlock instant, AI-driven research and patent intelligence for your innovation.

Process for preparing optically active beta-hydroxyketone

A hydroxy ketone, photoactive technology, applied in the field of chiral compound preparation chemistry, can solve the problems of low enantioselectivity, and achieve the effects of high enantiomeric purity, mild reaction conditions, and simple and easy-to-obtain raw materials

Inactive Publication Date: 2006-09-06
WUHAN UNIV
View PDF0 Cites 5 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the enantioselectivity of L-proline in catalyzing the direct aldol addition reaction of aromatic aldehydes and ketones is relatively low

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019]Inject 3ml (40mmol) acetone into a test tube containing magneton, 1.5mmol (S)-proline, 1mmol (R)-1,1'-bi-2-naphthol, stir at 40°C for 15min, Then 5 mmol benzaldehyde was added and stirring was continued at this temperature for 48 h. Add 10ml saturated NH 4 Cl aqueous solution, stirred for 5min, extracted with ethyl acetate (15ml×3), combined organic phases, anhydrous Na 2 SO 4 Drying, concentration, column chromatography (silica gel, 200-300mesh, petroleum ether: acetone (v / v) = 2:1) to obtain (R)-4-hydroxy-4-phenyl-2-butanone, yield: 52.4%; [α] D 20 +55.8 (c=2.3, in CHCl 3 ), 91.3%ee; 1 H NMR (CDCl 3 , 300MHz) δ (ppm): 7.33-7.25 (m, 5H, Ph-H), 5.14-5.11 (d, J = 6.7Hz, 1H, CH), 3.57 (s, 1H, OH), 2.92-2.74 ( m, 2H, CH 2 ), 2.17 (s, 3H, CH 3 ); 13 C NMR (CDCl 3 , 300MHz) δ (ppm): 209.2, 143.0, 128.7, 127.9, 125.8, 70.1, 52.3, 31.1; IR (KBr): v 3420 (s, OH), 3031 (w, Ph-H), 2902 (w, CH), 1708 (vs, C=O), 1602 (w, Ph-H).

Embodiment 2

[0021] Inject 5ml (68mmol) acetone into a test tube containing magneton, 1.5mmol (S)-proline, 1mmol (R)-1,1'-bi-2-naphthol, and stir at 20°C for 15min, Then add 5mmol benzaldehyde and stir the reaction at 40°C for 96h. Add 10ml saturated NH 4 Cl aqueous solution, stirred for 5min, extracted with ethyl acetate (15ml×3), combined organic phases, anhydrous Na 2 SO 4 Drying, concentration, column chromatography (silica gel, 200-300mesh, petroleum ether: acetone (v / v) = 2:1) to obtain (R)-4-hydroxy-4-phenyl-2-butanone, yield: 56.0%; [α] D 20 +54.0 (c=2.0, in CHCl 3 ), 88.3%ee.

Embodiment 3

[0023] Inject 3ml (40mmol) acetone into a test tube containing magnetons, 2.0mmol (S)-proline, 1mmol (R)-1,1'-bi-2-naphthol, and stir at -20°C for 15min , Then add 5mmol benzaldehyde and continue stirring at this temperature for 8h. Add 10ml saturated NH 4 Cl aqueous solution, stirred for 5min, extracted with ethyl acetate (15ml×3), combined organic phases, anhydrous Na 2 SO 4 Drying, concentration, column chromatography (silica gel, 200-300mesh, petroleum ether: acetone (v / v) = 2:1) to obtain (R)-4-hydroxy-4-phenyl-2-butanone, yield: 49.1%; [α] D 20 +53.1 (c=1.7, in CHCl 3 ), 86.9%ee.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention relates to a method for preparation ofª‰-hydroxyketone with optical activity. It consists of adding aldehyde after mixing the acetone and the chiral diol or the chiral diphenol at the temperature of -20-110 DEG C in the organic solvent with the (s)-proline, and stirring the solution for 8-96 hours; and obtaining the chiral beta-hydroxyketone by the purifying the reaction product. The invention selectively obtains the chiral beta-hydroxyketone by a step that the simple organic molecule catalyzes the asymmetric aldol with a high selectivity and it is dramatically characterized in that its chiral activator is cheap and easy to get, its reaction condition is mild, its craft is easy, its raw material is simple, its atom utilization efficiency is high, its cost is low, and its purity of enantiomer is high.

Description

technical field [0001] The invention describes the preparation of photoactive β-hydroxyketone through catalyzed direct asymmetricaldol addition and high enantioselectivity, and belongs to the field of chiral compound preparation chemistry. Background technique [0002] Photoactive β-hydroxyketones are important chiral compounds with two typical functional groups, and they are widely used in the preparation of chiral drugs and natural products. [0003] Aldol addition reaction is an important method to prepare photoactive β-hydroxy ketones. This method is divided into two types: Mukaiyama type aldol reaction and direct aldol reaction. The Mukaiyama type aldol reaction is to convert a relatively poorly reactive ketone into a highly reactive enolate by reacting with a metal reagent, a silicon reagent or a boron reagent in advance, and then add it to an aldehyde in a chiral environment and then hydrolyze it to obtain a chiral β -Hydroxyketones. This method requires relatively ...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/00C07C45/64C07C49/00
Inventor 单自兴周炎
Owner WUHAN UNIV