Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

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
View PDF0 Cites 4 Cited by
  • Summary
  • 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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • 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.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
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
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com