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Method for synthesizing optical activity 2,3-allenes secondary alcohol

An optically active, secondary alkenyl alcohol technology, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve the problems of expensive, difficult to obtain reagents or catalysts, etc., and achieve simple operation, convenient mass preparation, and convenient reagents Easy to get effect

Inactive Publication Date: 2009-08-12
ZHEJIANG UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But the reagent of method (1)-(4) or catalyzer are difficult for obtaining or more expensive, although method (5) can be prepared in a large amount, the substituting group of 1 is subjected to bigger restriction (substituting group can only be to contain 1-2 carbon group)

Method used

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  • Method for synthesizing optical activity 2,3-allenes secondary alcohol
  • Method for synthesizing optical activity 2,3-allenes secondary alcohol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Add tetrahydrofuran (50mL), (S)-1-phenyl-2-propynol (1.3166g, 10.0mmol, enantiomeric excess value 99.6%) to a three-neck flask treated with anhydrous and oxygen-free at room temperature , then dropwise added n-butyllithium (8.8mL, 2.5M inhexanes, 22.0mmol) at -78°C, continued the reaction for half an hour after the dropwise addition, and then added dropwise chloromethyl ether (1.14mL, d=1.06g / mL , 1.21g, 15.0mmol), after reacting for 19 hours, dot the plate to follow the reaction of raw materials completely, add 10mL saturated ammonium chloride solution to quench, extract with 20mL diethyl ether each time, extract three times, wash once with 20mL saturated saline, dry over anhydrous sodium sulfate , filtered, concentrated, and subjected to flash column chromatography to obtain 1.1139 g of the product (R)-4-hydroxy-4-phenyl-2-butynyl methyl ether, with a yield of 63%. The product is a colorless liquid. Product enantiomeric excess: 98.2%, measured by HPLC:

[0020] (HPL...

Embodiment 2

[0022] According to the method described in Example 1, the difference is that the substrate and reagent used are: (R)-1-phenyl-2-propynol (0.6604g, 5.0mmol, enantiomeric excess value 99.9%), normal Butyllithium (4.4mL, 2.5M in hexanes, 11.0mmol) and chloromethyl ether (0.58mL, d=1.06g / mL, 0.615g, 7.5mmol) were reacted in 25mL tetrahydrofuran for 16 hours to obtain the product (S)-4 -Hydroxy-4-phenyl-2-butynyl methyl ether 0.5778g, yield 66%. The product is a colorless liquid. Product enantiomeric excess: 96.1%, measured by HPLC:

[0023] (HPLC condition: Chiralcel AD-H, n-hexane / i-PrOH=90 / 10, 0.8mL / min, λ=230nm, t R 11.7 (major), 13.6 (minor)); [α] 20 D =-16.0° (c=0.70, CHCl 3 ); 1 H NMR (300MHz, CDCl 3 )δ 7.58-7.50(m, 2H), 7.43-7.30(m, 3H), 5.52(d, J=6.0Hz, 1H), 4.19(d, J=1.5Hz, 2H), 3.40(s, 3H) , 2.36 (bs, 1H).

Embodiment 3

[0025] According to the method described in Example 1, the difference is that the substrate and reagent used are: (S)-1-p-methylphenyl-2-propynyl alcohol (0.4642g, 3.2mmol, enantiomeric excess value 99.9% ), n-butyllithium (2.8mL, 2.5M in hexanes, 7.0mmol) and chloromethyl ether (0.36mL, d=1.06g / mL, 0.382g, 4.8mmol) were reacted in 20mL tetrahydrofuran for 14.5 hours to obtain the product (R )-4-hydroxy-4-p-methylphenyl-2-butynyl methyl ether 0.4034 g, yield 67%. The product is a colorless liquid. Product enantiomeric excess: 99.2%, measured by HPLC:

[0026] (HPLC condition: Chiralcel AD-H, n-hexane / i-PrOH=90 / 10, 0.8mL / min, λ=230nm, t r 15.3 (major), 12.7 (minor)); [α] 20 D =+16.4° (c=0.80, CHCl 3 ); 1 HNMR (300MHz, CDCl 3 )δ 7.43(d, J=8.1Hz, 2H), 7.19(d, J=8.1Hz, 2H), 5.49(d, J=6.3Hz, 1H), 4.19(d, J=1.5Hz, 2H), 3.40(s, 3H), 2.36(s, 3H), 2.21(d, J=6.3Hz, 1H); 13 C NMR (75MHz, CDCl 3 )δ 137.9, 137.6, 129.0, 126.4, 86.6, 81.6, 64.0, 59.7, 57.4, 21.0; IR (neat) v (cm ...

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Abstract

The invention relates to a synthetic method of optical activity 2, 3-allenes disubstituted carbinol with high enantiomeric excess; optical activity propiolic alcohol reacts with n-butyllithium and chloromethyl ether to generate optical activity 4- hydroxyl-4- aryl-2- butynyl methyl ether which then reacts with grignard reagent (ethyl ether solution) under the catalysis of cuprous bromide, so that the optical activity 2, 3-allenes disubstituted carbinol with high enantiomeric excess can be synthesized. The operation of the method is simple, the raw materials and the reagents are easy to obtain, and the product has high enantioselectivity. The method can simultaneously introduce multiple substitutional groups which are easy to separate and purify, so as to be applicable to synthesizing various substitutional optical activity 2, 3-allenes disubstituted carbinols.

Description

technical field [0001] The present invention relates to a method for synthesizing optically active 2,3-alkenyl secondary alcohols with high enantiomeric excess. Background technique [0002] 2,3-alkenyl secondary alcohol is one of the most important precursors in organic synthesis, and is often used in organic reactions to synthesize 2,5-dihydrofuran, epoxy compounds, 3-halogen-3-enal, etc. Optically active 2,3-alkenyl secondary alcohols are important precursors of various optically active organic compounds. The existing methods for synthesizing optically active 2,3-alkenyl secondary alcohols are usually: (1) chiral reduction of α-alkenone; (2) addition of chiral propargyl or allenyl metal reagents to aldehydes reaction; (3) Crabbé reaction of optically active propynyl alcohol; (4) addition reaction of propargyl or allenyl metal reagent and aldehyde with participation of chiral ligand; (5) enzyme racemic 2,3- Kinetic resolution of allenic secondary alcohols. But the reage...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C33/30C07C29/44C07C29/00
Inventor 李晶周超傅春玲麻生明
Owner ZHEJIANG UNIV
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