Chiral allyl ester compound and preparation method thereof

A technology for compounds and allyl esters, applied in the field of organic chemical synthesis, can solve the problems of low optical purity of target products, difficulty in obtaining enantioselectivity, low yield of target products, etc., and achieves a wide range of substrates and easy-to-obtain catalysts. , the effect of good yield

Inactive Publication Date: 2015-03-11
TONGJI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] In 2010, Onitsuka reported that ruthenium catalyzed the allylation reaction of allyl chloride as a substrate, and obtained chiral allyl esters efficiently (N.Kanbayashi, K.J.Onitsuka, Am.Chem.Soc.2010, 132, 1206-1207 ), however, the preparation of the catalyst for this reaction requires more than 10 delicate operations, which seriously hampers its practical application
However, as in previous studies, it is difficult to obtain ideal enantioselectivity for the more reactive allyl halide as the substrate, for example, the optical purity is only 57% when allyl chloride is used as the substrate ((a) Bartels, B.; Yebra, C.; Rominger, F. Helmchen, G. Eur. J. Inorg. Chem. 2002, 34, 2569. (b) Madrahimovand, S. T.; Hartwig, J. F. J. Am. Chem. Soc.2012, 134, 8136)
[0007] It can be seen that the existing asymmetric catalytic synthesis method of allyl ester not only has a low yield of the target product, but also has low optical purity of the target product, so it is difficult to apply on a large scale

Method used

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  • Chiral allyl ester compound and preparation method thereof
  • Chiral allyl ester compound and preparation method thereof
  • Chiral allyl ester compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] In a dry reaction tube protected by argon, 0.002 mmol of dibenzo-1,5-cyclooctadiene iridium chloride dimer, 0.004 mmol of chiral ligand L, 1,4-diazabicyclo [2.2.2] Octane 0.002mmol and dioxane 1mL were reacted at 30°C for 0.2h to prepare an iridium catalyst.

[0047] Add 0.2 mmol of potassium acetate to the catalytic system, then add 0.22 mmol of allyl halide, 0.2 mmol of KCl, and 2.0 mL of THF, and stir at room temperature for 6 hours. After the reaction is completed, pass through a diatomite sand core and remove the solvent under reduced pressure. Chromatography yielded the target product 1 (petroleum ether / ethyl acetate=40 / 1).

[0048] Target product 1: (S)-1-phenylallyl ethyl ester

[0049]

[0050] Yellow liquid, 91% yield, 94%ee [chiral column OJ-H (0.46cm x 25cm); n-hexane / isopropanol=95 / 5; flow rate=0.6mL / min; detection wavelength=214nm; t R =21.012(minor), 23.24l(major)min].

[0051] HRMS (ESI + )calcd for C 11 h 12 NaO 2 [M+Na] + : 199.0735, Found: ...

Embodiment 2

[0053] In a dry reaction tube protected by argon, add 1,5-cyclooctadiene (H 5 -indene)iridium 0.001mmol, chiral ligand L 0.002mmol, isopropylamine 0.002mmol and tetrahydrofuran 1mL, react at 40°C for 0.4h.

[0054] Add 0.2mmol of potassium acetate to the catalytic system, then add 0.4mmol of allyl halide, 0.2mmol of CsCl, and 2.0mL of diethyl ether, stir at room temperature for 2h, after the reaction is completed, filter, and then distill to remove low boilers to obtain the target product 2 .

[0055] Target product 2: (S)-1-p-methoxyphenyl allyl ethyl ester

[0056]

[0057] Yellow liquid, 92% yield, 95%ee [chiral column OJ-H (0.46cm x 25cm); n-hexane / isopropanol=95 / 5; flow rate=0.6mL / min; detection wavelength=214nm; t R = 18.12 (minor), 19.24 (major) min].

[0058] HRMS (ESI + )calcd for C 11 h 12 NaO 2 [M+Na] + : 229.0841, Found: 229.0844.

Embodiment 3

[0060] In a dry reaction tube protected by argon, 0.0015 mmol of 1,5-cyclooctadiene iridium chloride dimer, 0.003 mmol of chiral ligand L, 1,8-diazabicyclo[5.4. 0] Undec-7-ene 0.003mmol and THF 1.5mL were reacted at 80°C for 0.5h.

[0061] Add 0.2mmol of sodium acetate to the catalytic system, then add 0.4mmol of allyl halide, 0.2mmol of CsF, and 2.0mL of acetonitrile, and stir at 120°C for 2h. The target product 3 was obtained by recrystallization of cyclohexane at 5°C.

[0062] Target product 3: (S)-1-p-methylphenylallyl ethyl ester

[0063]

[0064] Colorless liquid, 93% yield, 91%ee [chiral column OJ-H (0.46cm x 25cm); n-hexane / isopropanol=95 / 5; flow rate=0.6mL / min: detection wavelength=214nm; 1 R = 11.52 (minor), 12.93 (major) min].

[0065] HRMS (ESI + )calcd for C 11 h 12 NaO 2 [M+Na] + : 213.0891, Found: 213.0864.

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Abstract

The invention relates to a chiral allyl ester compound and a preparation method thereof. The structural formula of the chiral allyl ester compound is represented in the description. The preparation method comprises the following steps: adding raw materials (carboxylate and allyl halide) into an organic solvent, then adding an iridium catalyst, which is prepared by reacting an iridium complex with a ligand, adding additives, controlling the reaction temperature in a range of 0 to 120 DEG C, carrying out reactions for 1 to 36 hours, and separating the reaction products so as to obtain the chiral allyl ester compound. In the prior art, when active allyl halide is taken as the substrate, the reaction yield is low and the enantioselectivity is bad, and the provided preparation method overcomes the problems mentioned above. Moreover the preparation method has the characteristics of high reaction yield, good region-selectivity, and high enantioselectivity, and thus is widely used in the organic synthesis methodology and natural product synthesis.

Description

technical field [0001] The invention belongs to the technical field of organic chemical synthesis, and relates to a chiral allyl ester compound and a preparation method thereof, in particular to a chiral iridium complex as a catalyst, through allyl halide and carboxylate high region Selective and highly enantioselective synthesis of chiral allyl esters. Background technique [0002] Chiral allyl esters and their hydrolysis products chiral allyl alcohols are a class of compounds with high biological activity. As an important fragment of many organic compounds, it is widely used in organic chemistry, medicine, pesticide, chemical industry and other fields. [0003] Currently, chiral allyl esters are mainly prepared by kinetic resolution (Y.Gao, R.M.Hanson, J.M.Klunder, H.Masamune, K.B.Sharpless, J.Am.Chem.Soc. 1987, 109, 5165-5180). There are few studies on the direct synthesis of optically pure allyl esters via asymmetric catalysis. [0004] In 2010, Onitsuka reported that...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/145C07C67/04C07C69/16C07C69/24C07D333/38C07D213/30C07C69/54C07C69/56C07D309/32C07C69/618C07C67/343B01J31/22C07F15/00
CPCB01J31/186B01J2231/44B01J2531/0213B01J2531/827C07C67/11C07C67/343C07C69/007C07C69/157C07C69/16C07C69/24C07C69/54C07C69/56C07C69/618C07D213/30C07D309/30C07D309/32C07D333/38
Inventor 赵晓明刘海征张敏蔡君美郑璞睿
Owner TONGJI UNIV
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