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Method of preparing chiral primary alcohol and secondary alcohol with chirality center at ortho position of hydroxyl group

A chiral, ortho-position technology, applied in the preparation of hydroxyl compounds, organic compounds, chemical instruments and methods, etc., to achieve the effects of high reactivity, high conversion number, and high optical yield

Inactive Publication Date: 2007-10-24
NANKAI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, such synthetic methods are rarely used to synthesize chiral β-aryl primary alcohols which are widely used in chiral drugs and natural products.

Method used

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  • Method of preparing chiral primary alcohol and secondary alcohol with chirality center at ortho position of hydroxyl group
  • Method of preparing chiral primary alcohol and secondary alcohol with chirality center at ortho position of hydroxyl group
  • Method of preparing chiral primary alcohol and secondary alcohol with chirality center at ortho position of hydroxyl group

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preparation example Construction

[0020]The method for preparing chiral primary alcohols and secondary alcohols having a chiral center at the ortho position of the hydroxyl group described in the present invention is realized by a chiral bisphosphine-ruthenium-bisamine catalyst having the general formula III under the condition of the presence of a base. The catalyst includes a chiral bisphosphine ligand with a general formula IV with a spiro ring skeleton and a well-known bisphosphine ligand with a general formula V with a biaryl ring skeleton. The chiral diamine used in the catalyst is a chiral diamine compound with general formula VI.

[0021]

[0022] In formula III,

[0023] Y and Y' are respectively Cl, Br, I or H, and Y and Y' may be the same or different.

[0024] Chiral bisphosphine ligands shown in general formula III include chiral bisphosphine compounds having general formulas IV and V.

[0025]

[0026] In formulas IV and V,

[0027] n=0~4; R 1 , R 2 for H, C 1 ~C 10 Alkyl, C 1 ~C 1...

Embodiment 1

[0042] Preparation of chiral bisphosphine-ruthenium-bisamine catalyst ((S)-7,7'-bis-(bis-(4-methoxy-3,5-dimethylphenyl)-phosphino)-1 , 1′-spirodihydroindane (DMM-SDP) and (R, R)-1,2-cyclohexanediamine ((R, R)-DACH) and [RuCl 2 (C 6 h 6 )] 2 Complexation preparation (RuCl 2 -(S)-Xyl-SDP / (R,R)-DACH) as an example)

[0043] In a nitrogen atmosphere, (S)-7,7'-bis-(bis-(4-methoxy-3,5-dimethylphenyl)-phosphino)-1,1'-spirodihydroindane (DMM-SDP) (141.9mg, 0.165mmol) and [RuCl 2 (C 6 h 6 )] 2 (40mg, 0.08mmol) was dissolved in 3mL DMF, heated to 100°C, stirred for 3.0 hours, after a little cooling, added (R,R)-1,2-cyclohexanediamine ((R,R)-DACH) (18.8 mg, 0.165 mmol). After stirring at room temperature for 18 hours, the solution was removed in vacuo to obtain a reddish-brown solid. The solid was used directly in the hydrogenation reaction.

[0044] The other chiral bisphosphine-ruthenium-bisamine catalysts were prepared in the same way.

Embodiment 2

[0046] Asymmetric Catalytic Hydrogenation of α-Aryl Aldehydes to Synthesis of Chiral β-Aryl Primary Alcohols

[0047] Add 0.002mmol of catalyst, 2mmol of α-arylaldehyde, 0.04mmol of potassium tert-butoxide and 8mL of isopropanol into a hydrogenation reactor, and stir the hydrogenation reaction at room temperature for 8-24 hours under a hydrogen pressure of 50 atm. The solvent was removed under reduced pressure, and the target product was obtained through silica gel column chromatography. The conversion rate and optical purity of the product were analyzed by GC or HPLC, and the results are shown in Table 1.

[0048] Table 1.

[0049]

[0050] α-Arylaldehyde

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Abstract

The invention discloses a making method of application of chiral primary alcohol and secondary alcohol with chiral center adjacent to optical active hydroxy, which is characterized by the following: proceeding corresponding selectivity catalytic and hydrogenating for racemic alpha-substituted fat aldehydo and ketone; fitting for preparing the product with corresponding selectivity over 99. 9%ee through chiral toroid diphosphine-ruthenium-diamine as catalyst; using the product as chiral intermediate to synthesize fenvalerate, BAYX1005 and some natural products.

Description

technical field [0001] The invention relates to a simple and suitable preparation method and application of chiral primary alcohols and secondary alcohols having a chiral center at the ortho position of an optically active hydroxyl group. Background technique [0002] Asymmetric catalytic hydrogenation of prochiral compounds containing carbon-carbon double bonds, carbon-oxygen double bonds, and carbon-nitrogen double bonds is an important synthetic method for atom-economical and environmentally friendly asymmetric catalytic synthesis of chiral compounds. Among the asymmetric catalytic hydrogenation reactions of these prochiral substrates, the asymmetric catalytic hydrogenation of carbonyl-containing compounds such as ketoesters, aromatic ketones, etc. is one of the hot research fields in current organic synthetic chemistry, and has been received by people. Attention (Ohkuma, T.; Kitamura, M.; Noyori, R. Catalytic Asymmetric Synthesis, Wiley, New York, 2000). In the asymmetr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C33/20C07C29/141C07C29/145B01J31/24B01J31/28
Inventor 周其林谢建华周章涛刘盛孔维玲王立新
Owner NANKAI UNIV
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