Method for synthesizing beta-functionalized multi-substituted allyl alcohol

A technology of functional grouping and allyl alcohol, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve problems such as low selectivity, difficulty in repeating, inapplicability of secondary Grignard reagents, etc., and achieve easy The effect of separation and purification

Inactive Publication Date: 2008-01-09
ZHEJIANG UNIV
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Problems solved by technology

Previous literatures have reported that carbon metallation reactions synthesize β-functionalized allyl alcohols. Generally, acetylenic alcohols are used as substrates, and only primary alcohols can be obtained, while the reaction regioselectivity of secondary or tertiary acetylenic alcohols is not high or only α-functional groups are formed. allyl alcohols; it has been reported in the past that the carbometallation reaction of allenols generally uses the simplest allenols as substrates, or selects highly active allyl metal reagents. There is an example (R.Gelin, M Albrand, C.R.Acad .Sc.Paris.Serie C.1976, 283,755.) Carbometallation reaction of substituted allenols, but the conditions described are difficult to repeat, Chinese patent 200510061283, synthesis of α-functionalized multi-substituted allyl alcohols A method for the high regio- and stereoselective synthesis of α-functionalized polysubstituted allyl alcohols by carbometallation of acetylenic alcohols is disclosed
However, the above method is not suitable for secondary Grignard reagents, and the selectivity of aryl Grignard reagents is general

Method used

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  • Method for synthesizing beta-functionalized multi-substituted allyl alcohol
  • Method for synthesizing beta-functionalized multi-substituted allyl alcohol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Under nitrogen, add cuprous chloride (0.1974g, 2.0mmol), 2-butyl-2,3-butadien-1-ol (0.1244g, 1.0mmol) and ether (1.5mL), cool to minus seven Eighteen degrees, dropwise added to the ether solution (5mL, 5mmol) containing amyl Grignard reagent, after the addition, slowly return to room temperature, react overnight, then cool to minus seventy-eight degrees, dropwise add iodine (1.0g , 4 mmol) in tetrahydrofuran solution, the reaction was completed under stirring for 0.5 hours, and saturated sodium thiosulfate was added dropwise to eliminate excess iodine. Extracted with ether, washed with saturated sodium thiosulfate, 5% hydrochloric acid, saturated sodium bicarbonate, and saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and flash column chromatography gave 0.2254 g of the product with a yield of 70 %. The product is a colorless liquid.

[0026] 1 H NMR (400MHz, CDCl 3 )δ4.22(s, 2H), 2.54(t, J=7.6Hz, 2H), 2.30(t, J=8.0Hz, 2H), 1.68(bs, 1H),...

Embodiment 2

[0031] Under nitrogen, add cuprous chloride (0.1975g, 2.0mmol), 3-butyl-3,4-pentadien-2-ol (0.1401g, 1.0mmol) and ether (1.5mL), cool to minus seven Eighteen degrees, dropwise added to the ether solution containing amyl Grignard reagent (5mL, 5mmol), after the addition, slowly return to room temperature, react overnight, then cool to minus five degrees, dropwise add iodine (1.27g, 5mmol ) THF solution, the reaction was complete under stirring for 0.5 hour, and saturated sodium thiosulfate was added dropwise to eliminate excess iodine. Extracted with ether, washed with saturated sodium thiosulfate, 5% hydrochloric acid, saturated sodium bicarbonate, and saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and flash column chromatography gave the product 0.1908g with a yield of 56 %. The product is a colorless liquid.

[0032] 1 H NMR (400MHz, CDCl 3 )δ4.77(q, J=6.3Hz, 1H), 2.55-2.43(m, 2H), 2.30-2.20(m, 1H), 2.20-2.10(m, 1H), 1.67(bs, 1H), 1.58 -1....

Embodiment 3

[0034] According to the method described in Example 2, the difference is that the substrate used and the reagent are: cuprous chloride (0.1998g, 2.0mmol), S-3-butyl-3,4-pentadien-2-alcohol ( 0.1401g, 1.0mmol, ee=98%) the diethyl ether solution (5mL, 5mmol) of pentyl Grignard reagent, iodine (1.3017g, 5mmol), obtains the S configuration product 0.2745g, and yield rate is 81% (ee=98%) %). The product is a colorless liquid.

[0035] 1 H NMR (400MHz, CDCl 3)δ4.77(q, J=6.3Hz, 1H), 2.55-2.43(m, 2H), 2.30-2.20(m, 1H), 2.20-2.10(m, 1H), 1.67(bs, 1H), 1.58 -1.50(m, 2H), 1.50-1.26(m.10H), 1.23(d, J=6.3Hz, 3H), 0.95-0.85(m, 6H); 13 C NMR (CDCl 3 , 100MHz) δ145.4, 105.6, 77.7, 41.1, 33.0, 31.7, 29.7, 28.2, 27.6, 23.1, 22.6, 20.8, 14.0, 13.8; MS (m / z) 338 (M + , 1.69), 211 (M + -I, 23.07), 43 (100); IR (neat, cm -1 )3373, 2957, 2926, 2858, 1618, 1465, 1378, 1111, 1060; HRMS calcd for C 14 h 27 OI 338.1107, found 338.1115.

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Abstract

A beta-functional group multi-substituted 1-propen-3-ol and its synthesis are disclosed. The process is carried out by carbon-metal reacting Grignard reagent with diolefine to generate carbon-carbon bond and carbon-metal bond, and reacting with various reagents to obtain a series of beta-functional group multi-substituted propen compound. It's simple and easy, has better regional and spatial selectivity and can be used for various substituted propens.

Description

technical field [0001] The invention relates to a method for synthesizing β-functionalized multi-substituted allyl alcohols, that is, a method for synthesizing β-functionalized multi-substituted allyl alcohols with high regioselectivity and stereoselectivity through carbometallation of allenols. Background technique [0002] β-functionalized multi-substituted allyl alcohol is one of the most important intermediates in organic synthesis and one of the most common structural units in natural products. It has a variety of important physiological activities and is widely used in biotechnology, medicine and pesticides It has huge development and utilization value. Previous literatures have reported that carbon metallation reactions synthesize β-functionalized allyl alcohols. Generally, acetylenic alcohols are used as substrates, and only primary alcohols can be obtained, while the reaction regioselectivity of secondary or tertiary acetylenic alcohols is not high or only α-functio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C33/03C07C33/38C07C29/32
Inventor 麻生明陆展
Owner ZHEJIANG UNIV
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