Method for stereoselective synthesis of (E)-trisubstituted olefin

A stereoselective, three-substitution technology, which is applied in the preparation of halogenated hydrocarbons, organic chemical methods, chemical instruments and methods, etc., can solve the problems of expensive catalyst, large amount of catalyst, and long reaction time, etc., and achieve high industrial application prospects, Great practical application value, high stereoselective effect

Active Publication Date: 2020-03-24
WENZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] (1) The catalyst is expensive, and it is a noble metal catalyst such as ruthenium, rhodium, palladium, and some also need complex ligands or active metal complexes;
[0006] (2) The catalytic efficiency is low, the reaction time is long (5-29 hours), and the consumption of catalyst is large (2-5mol%);
[0007] (3) The reaction conversion rate is low, and the stereoselectivity is relatively poor;
[0008] (4) The substrates are limited, and there are few application examples, and only aryl-substituted substrates are applicable;
In particular, it should be noted that in drug molecules, the difference in configuration may lead to differences in the effect or even the opposite

Method used

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  • Method for stereoselective synthesis of (E)-trisubstituted olefin
  • Method for stereoselective synthesis of (E)-trisubstituted olefin
  • Method for stereoselective synthesis of (E)-trisubstituted olefin

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Embodiment 1: Synthesis of E-trisubstituted olefins by catalytic isomerization

[0044]

[0045] Reaction operation: at 25°C, add CoCl to a dry reaction test tube 2 (0.01mmol), PAO ligand (0.01mmol), alkene (10mmol), toluene (1mL), injected into triethylsodium borohydride (0.03mmol), then stirred at room temperature for 10 minutes and separated by column chromatography to obtain the product .

[0046] Product 1: (E)-1-(But-2-en-2-yl)-4-methoxybenzene

[0047]

[0048] Colorless oily liquid, yield>99%, E / Z>99 / 1. 1 H NMR: (400.0MHz, CDCl 3 )δ7.33-7.28(m,2H),6.87-6.82(m,2H),5.83-5.73(m,1H),3.80(s,3H),2.03-1.98(m,3H),1.78(dq, J=6.8,1.2Hz,3H).

[0049] Product 2: (E)-1-(But-2-en-2-yl)-3-methoxybenzene.

[0050]

[0051] Colorless oily liquid, yield>99%, E / Z>99 / 1. 1 H NMR: (400.0MHz, CDCl 3 )δ7.22(t, J=7.8Hz, 1H), 6.97(d, J=7.8Hz, 1H), 6.93-6.89(m, 1H), 6.79-6.74(m, 1H), 5.91-5.83(m ,1H),3.81(s,3H),2.01(s,3H),1.79(dq,J=6.8,1.0Hz,3H).13C NMR:(100.6MHz,CDCl3)d...

Embodiment 2

[0115] Embodiment 2: the asymmetric epoxidation reaction comparison of three substituted alkenes

[0116]

[0117] Reaction operation: at room temperature, in a dry reaction test tube, add Salen-Mn catalyst (0.05mmol), olefin (1mmol), dichloromethane (DCM) (2mL), sodium hypochlorite (NaOCl) (1.5mmol), then After stirring for 3 hours at °C, the product was isolated by column chromatography.

[0118] The reaction using the E / Z-trisubstituted olefin mixture (E / Z=20 / 80) as the raw material gives the mixed product of the epoxidation reaction in a ratio of 1:4. The reaction starting from E-trisubstituted alkenes (E / Z>99 / 1) gave product 24.

[0119] Product 24: (2S,3S)-2,3-dimethyl-2-phenyloxirane

[0120]

[0121] Colorless oily liquid, yield 82%, 93% ee. 1 HNMR: (400.0MHz, CDCl 3 )δ7.20-7.37 (m, 5H), 2.97 (q, J = 5.6Hz, 1H), 1.69 (s, 3H), 1.45 (d, J = 5.4Hz, 3H); 13 C NMR (100MHz, CDCl 3 )δ: 143.5, 128.7, 127.6, 125.4, 62.9, 60.6, 17.8, 14.9.

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PUM

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Abstract

Belonging to the technical field of metal catalytic synthesis, the invention discloses a method for stereoselective synthesis of (E)-trisubstituted olefin. The method includes: taking 1, 1-disubstituted olefin as the raw material, and adopting a combination of CoX2 and PAO ligand as the catalyst; and in the presence of an activating reagent, carrying out reaction for 0.5min-48h at a temperature ranging from -30DEG C to 80DEG C to prepare (E)-trisubstituted olefin. Compared with the prior art, the method has the advantages of more economical, efficient and environment-friendly catalyst, good tolerance of the reaction functional group, mild reaction conditions, simple operation, no need for participation of additional reagents, and atom economy of 100%. In addition, the reaction has no needof any other toxic transition metal (like ruthenium, rhodium, palladium, etc.) salt, therefore the method has great practical application value in pharmaceutical and food chemical industry.

Description

technical field [0001] The invention belongs to the technical field of metal catalytic synthesis, and in particular relates to a method for stereoselectively synthesizing (E)-trisubstituted olefins. Background technique [0002] Currently, the closest prior art: Trisubstituted alkenes are widely found in natural products and are also important synthons, which are used in asymmetric hydrogenation reactions, allylation reactions, and conjugate addition reactions. Trisubstituted alkenes can be prepared by classical methods such as Wittig reaction, alkene metathesis, and coupling reactions. However, the trisubstituted alkenes synthesized by these methods are usually a mixture of E configuration and Z configuration, and trisubstituted alkenes with a single stereo configuration cannot be obtained. Although the E configuration and Z configuration of the same olefin have the same molecular composition and similar physical and chemical properties, the difference in configuration mak...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C41/32C07C43/215C07C5/25C07C15/44C07C15/50C07C209/68C07C211/48C07F7/18C07C319/20C07C321/28C07C67/293C07C69/157C07C17/358C07C25/13C07C22/08C07C67/333C07C69/65C07C25/02C07D317/50C07D333/08C07D301/03C07D303/04
CPCC07B2200/07C07B2200/09C07C5/2562C07C15/44C07C15/50C07C17/358C07C22/08C07C25/02C07C25/13C07C41/32C07C43/215C07C67/293C07C67/333C07C69/157C07C69/65C07C209/68C07C211/48C07C319/20C07C321/28C07C2531/24C07D301/03C07D303/04C07D317/50C07D333/08C07F7/1804C07F7/1892
Inventor 陈建辉刘红梅蔡成丁洋浩刘波盛夏远志
Owner WENZHOU UNIVERSITY
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