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Method for synthesizing beta, gamma-polysubstituted beta, gamma-unsaturated alcohol

A multi-substitution and unsaturated technology, applied in the field of β synthesis, can solve the problems of inapplicability of secondary Grignard reagents, general selectivity and inapplicability of aryl Grignard reagents, etc. Stereoselective, easy-to-operate effects

Active Publication Date: 2009-09-16
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the past, it has been reported in the literature that metal carbonization reaction synthesizes functionalized allyl alcohol with terminal hydrogen or terminal alkyl substituted propargyl alcohol as a substrate, and only γ-hydrogen or alkyl substituted allyl alcohol can be prepared; in the literature ( Fleming, F.F.; Gudipati, V.; Steward, O.W.Org.Lett. 2002, 4, 659.) Metal carbonation of γ-cyano-substituted propargyl alcohols, but the conditions are not as good for secondary or tertiary propargyl alcohols Not applicable; Chinese patent 200510061283 method for synthesizing α-functionalized multi-substituted allyl alcohols discloses a method for synthesizing α-functionalized multi-substituted allyl alcohols with high regio and stereoselectivity through metal carbonization reaction of propargyl alcohol
However, the above method is not suitable for secondary Grignard reagents, the selectivity of aryl Grignard reagents is general, and the γ-position substituent is hydrogen; Chinese patent 200710068864 discloses a method for synthesizing β-functionalized multi-substituted allyl alcohols High regio- and stereoselective synthesis of β-functionalized polysubstituted allyl alcohols via metal carbonation of propargyl alcohols
However, the above method can only introduce alkyl substituents at the γ position

Method used

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  • Method for synthesizing beta, gamma-polysubstituted beta, gamma-unsaturated alcohol
  • Method for synthesizing beta, gamma-polysubstituted beta, gamma-unsaturated alcohol

Examples

Experimental program
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Effect test

Embodiment 1

[0024] Under nitrogen, add cuprous chloride (0.1005g, 1mmol), 4-phenyl-3-butyn-2-ol (0.1477g, 1mmol1) and toluene (1.5mL), cool to minus seventy-eight degrees, drop Add it to a THF solution (6 mL, 6 mmol) containing amyl Grignard reagent. After the addition is complete, slowly return to room temperature, react overnight, then cool to zero, and quench by adding saturated NH4Cl solution dropwise. It was extracted with ether, washed once with 5% hydrochloric acid, saturated sodium bicarbonate, and saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to flash column chromatography to obtain 0.1984 g of the product with a yield of 90%. The product is a colorless liquid.

[0025] 1 H NMR (300MHz, CDCl 3 )δ 7.36-7.38 (m, 2H), 7.27-7.18 (m, 3H), 6.56 (s, 1H), 4.42 (q, J=6.4Hz, 1H), 2.42-2.32 (m, 1H), 2.22- 2.10(m, 1H), 1.65-1.55(m, 1H), 1.55-1.43(m, 2H), 1.39(d, J=6.6Hz, 3H), 1.37-1.23(m, 4H), 0.91-0.83( m,3H); 13 C NMR (CDCl 3 , 75MHz) δ 1...

Embodiment 2

[0027] According to the method described in Example 1, the difference is that the substrates and reagents used are: cuprous chloride (0.0991g, 1mmol), 4-(2'-thiophene)-3-butyn-2-alcohol (0.1530g , 1mmol) and toluene (1.5mL) amyl Grignard reagent THF solution (6mL, 6mmol), to give the product 0.1881g, the yield was 83%. The product is a colorless liquid.

[0028] 1 H NMR (300MHz, CDCl 3 )δ 7.26-7.22 (m, 1H), 7.02-6.95 (m, 2H), 6.67 (s, 1H), 4.38 (q, J=6.3Hz, 1H), 2.54-2.42 (m, 1H), 2.34- 2.22(m, 1H), 1.70(bs, 1H), 1.60-1.47(m, 2H), 1.45-1.32(m, 7H), 0.91(t, J=7.1Hz, 3H); 13 C NMR (CDCl 3 , 75MHz) δ 145.1, 140.2, 127.2, 126.7, 124.9, 117.4, 72.4, 32.5, 29.3, 28.4, 22.5, 22.4, 14.1; IR (neat, cm -1 )3357, 2956, 2931, 2869, 1637, 1508, 1466, 1367, 1319, 1282, 1214, 1156, 1103, 1059, 1007; MS (m / z) 224 (M + , 28.70), 153(100); Elemental analysis calcd.for C 13 h 20OS: C, 69.59, H, 8.98; Found: C, 69.54, H, 8.96.

Embodiment 3

[0030] According to the method described in Example 1, the difference is that the substrates and reagents used are: cuprous chloride (0.0993g, 1mmol), 4-(2-pyridine)-3-butyn-2-alcohol (0.1471g, 1 mmol) THF solution of pentyl Grignard reagent (6 mL, 6 mmol) to obtain 0.1720 g of the product with a yield of 78%. The product is a colorless liquid.

[0031] 1 H NMR (300MHz, CDCl 3 )δ 8.59-5.55 (m, 1H), 7.62 (td, J=7.8 and J=2.1Hz, 1H), 7.21 (d, J=8.1Hz, 1H), 7.08 (ddd, J=7.5, 5.0and1. 2Hz, 1H), 6.60(s, 1H), 4.42(q, J=2.8Hz, 1H), 2.75-2.64(m, 1H), 2.40-2.28(m, 1H), 2.08(bs, 1H), 1.54 -1.44(m, 2H), 1.40(d, J=6.3Hz, 3H), 1.34-1.22(m, 4H), 0.86(t, J=7.1Hz, 3H); 13 C NMR (CDCl 3 , 75MHz) δ 156.9, 151.7, 149.1, 135.9, 123.8, 123.0, 120.9, 71.7, 32.2, 28.7, 28.6, 22.5, 22.3, 14.0; IR (neat, cm -1 )3379, 2957, 2929, 2868, 1648, 1586, 1563, 1468, 1429, 1367, 1291, 1152, 1118, 1059; MS (m / z) 219 (M + , 7.65), 158(100); HRMS calcd.for C 14 h 21 NONa(M + +Na): 242.1515; found: 242.1...

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Abstract

The invention discloses a method for synthesizing beta, gamma-polysubstituted beta, gamma-unsaturated alcohol. Grignard reagent is in the selective metal carbonization reaction with propargyl alcohol with aryl substituted terminal to obtain new carbon-to-carbon bond and carbon metal bond, a series of beta, gamma-polysubstituted beta, gamma-unsaturated alcohols are obtained by reacting with various Grignard reagents. The method has simple operation, easily available raw materials and reagents, the reaction has high region and stereo selectivity, a plurality ofsubstituents are introduced simultaneously, the product is easy to separate and purify and suitable for synthesizing various substituted beta, gamma-unsaturated alcohol.

Description

technical field [0001] The present invention relates to a method for synthesizing β, γ-multi-substituted β, γ-unsaturated alcohols, that is, highly regio- and stereoselectively synthesized β, γ by highly selective metal carbonization of propargyl alcohols substituted by terminal aryl groups - Polysubstituted β,γ-unsaturated alcohols. Background technique [0002] Allyl alcohol substituted by multifunctional groups 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 has huge potential in biotechnology, medicine and pesticides development and utilization value. In the past, it has been reported in the literature that metal carbonization reaction synthesizes functionalized allyl alcohol with terminal hydrogen or terminal alkyl substituted propargyl alcohol as a substrate, and only γ-hydrogen or alkyl substituted allyl alcohol can be prepared; ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/44C07C33/30C07C33/28C07C33/48C07C33/38C07D333/16C07D213/30C07C43/23C07C41/30
Inventor 张小兵傅春玲麻生明
Owner ZHEJIANG UNIV
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