Preparation of homoallylic alcohol compound and synthesis method and application thereof

A high allyl alcohol, synthesis method technology, applied in the direction of steroids, organic chemical methods, chemical instruments and methods, etc., can solve the problems of uneconomical and cumbersome methods, and achieve high selectivity, high reaction yield, and reaction The effect of short steps

Active Publication Date: 2020-12-25
DALIAN UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the tedious and uneconomical preparation method, which relies on preactivated allyl halides and stoichiometric metal reducing agents, limits its application.

Method used

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  • Preparation of homoallylic alcohol compound and synthesis method and application thereof
  • Preparation of homoallylic alcohol compound and synthesis method and application thereof
  • Preparation of homoallylic alcohol compound and synthesis method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032]

[0033] The experimental steps and purification methods were carried out according to the exploratory experiments. RF=0.4 (EA:PE=1:3), eluent: petroleum ether / ethyl acetate=20 / 1, the yield was 92%, and the product was a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.35–7.27(m,2H),7.24–7.17(m,3H),5.71(dt,J=17.2,9.8Hz,1H),5.23–5.08(m,2H), 4.28(q, J=7.1Hz, 2H), 3.62(dt, J=8.3, 4.2Hz, 1H), 2.88–2.58(m, 2H), 2.51–2.41(m, 1H), 2.40–2.24(m, 2H), 2.01(s, 1H), 1.84–1.65(m, 2H), 1.34(t, J=7.2Hz, 3H). 13 C NMR (101MHz, CDCl3) δ164.08(t, J=33.0Hz), 141.62, 135.77, 128.35, 128.29, 125.84, 118.55, 116.57(dd, J=249.2, 248.7Hz), 72.91, 62.67, 43.59(dd , J=4.3, 2.3Hz), 36.24, 35.89 (t, J=22.7Hz), 32.05, 13.73. 19 F NMR (377MHz, CDCl3) δ-101.44 (dt, J = 261.5, 15.0Hz, 1F), -105.06 (dt, J = 260.7, 17.9Hz, 1F). HRMS-ESI (m / z) [M+Na ] + calculated for C 17 h 22 f 2 NaO 3 ,335.1435,found 335.1431.

Embodiment 2

[0035] use replace The experimental steps and purification methods were carried out according to the exploratory experiments. RF=0.4 (EA:PE=1:3), eluent: petroleum ether / ethyl acetate=20 / 1, the yield was 71%, and the product was a colorless liquid. 1 H NMR (400MHz, CDCl3) δ5.75 (dt, J = 18.3, 9.3Hz, 1H), 5.24–4.97 (m, 2H), 4.26 (q, J = 7.1Hz, 2H), 2.76 (dd, J = 9.0,4.2Hz,1H),2.53(dq,J=9.1,4.6Hz,1H),2.47–2.16(m,2H),1.87(s,1H),1.32(t,J=7.1Hz,3H), 1.01–0.83(m,1H),0.68–0.40(m,2H),0.37–0.10(m,2H). 13 C NMR (101MHz, CDCl3) δ164.13(t, J=32.7Hz), 136.55, 118.19, 116.15(dd, J=251.7, 248.9Hz), 78.85, 62.64, 44.22(dd, J=4.9, 2.5Hz) ,35.87(t,J=22.8Hz),15.17,13.81,3.12,2.73. 19 F NMR (377MHz, CDCl3) δ-101.43 (dt, J = 261.5, 15.0Hz, 1F), -105.04 (dt, J = 260.7, 17.9Hz, 1F). HRMS-ESI (m / z) [M+Na ] + calculated for C 12 h 18 f 2 NaO 3 ,271.1122,found 271.1137.

Embodiment 3

[0037] use replace The experimental steps and purification methods were carried out according to the exploratory experiments. RF=0.4 (EA:PE=1:3), eluent: petroleum ether / ethyl acetate=20 / 1, the yield was 74%, and the product was a colorless liquid. 1H NMR (400MHz, CDCl3) δ5.77–5.51(m,1H),5.22–5.12(m,3H),4.27(q,J=7.1Hz,2H),4.21(dd,J=9.0,6.5Hz, 1H), 2.38(ddt, J=12.9, 6.2, 2.9Hz, 1H), 2.34–2.22(m, 1H), 2.21–2.07(m, 1H), 1.76(d, J=1.4Hz, 3H), 1.73 (dd,J=3.3,1.4Hz,1H),1.69(d,J=1.4Hz,3H),1.34(t,J=7.2Hz,3H). 13 C NMR (101MHz, CDCl3) δ164.10 (t, J = 32.8Hz), 137.74, 136.95, 124.51, 119.11, 116.06 (dd, J = 252.0, 249.0Hz), 69.95, 62.70, 44.94 (dd, J = 4.7 ,2.7Hz), 35.33(t, J=22.9Hz), 25.93, 18.48, 13.89. 19 F NMR (377MHz, CDCl3) δ-100.34(t, J=14.8Hz), -101.04(t, J=14.6Hz), -104.02(t, J=18.0Hz), -104.71(t, J=17.8Hz ).HRMS-ESI(m / z)[M+Na] + calculated for C 13 h 20 f 2 NaO 3 ,285.1278,found285.1268.

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Abstract

The invention provides a preparation of homoallylic alcohol compound and a synthesis method and application thereof, and belongs to the field of organic chemistry. Under the protection of inert gas atroom temperature and in the presence of an organic photosensitizer, a titanium catalyst and an electron donor, aldehyde or ketone reacts with a 1, 3-butadiene derivative and halogenated alkane underthe irradiation of blue light, and the homoallylic alcohol compound is obtained with high selectivity. The method has the advantages of mild reaction conditions, short reaction steps, simple post-treatment and high stereoselectivity and regioselectivity of reaction products. Meanwhile, the method can be used for derivatization of natural products.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and relates to a method for preparing homoallyl alcohol compounds, a synthesis method and an application thereof. Background technique [0002] Homoallylic alcohols are important building blocks for the synthesis of various pharmaceuticals and biologically active natural substances. The incorporation of allyl metal complexes on the carbonyl group is one of the most efficient methods to obtain homoallylic alcohols, which has promoted the rapid development of synthetic chemistry and medicinal chemistry in the past few decades. However, the tedious and uneconomical preparation methods relying on preactivated allyl halides and stoichiometric metal reducing agents limit their applications. Therefore, the development of a simple, economical and environmentally friendly synthetic method for homoallylic alcohol compounds, and its application to the synthesis of biologically active natural substances, wi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/732C07C67/343C07D307/54C07D309/10C07D333/60C07C43/178C07C41/30C07C33/48C07C29/38C07J9/00C07J17/00
CPCC07B2200/07C07C29/38C07C33/483C07C41/30C07C43/1787C07C67/343C07C69/732C07D307/54C07D309/10C07D333/60C07J9/005C07J17/00C07C2601/02
Inventor 石磊厉熙宇李富盛林爽杰陈昱清史彩哲
Owner DALIAN UNIV OF TECH
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