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A kind of alkenylated product of allyl alcohol urethane compound and its synthetic method

A technology of allyl alcohol urethane formic acid and ester compounds, which is applied in the preparation of organic compounds, steroids, organic chemical methods, etc., and achieves the effects of wide application prospects, mild reaction conditions, and simple operation

Active Publication Date: 2022-03-22
HANGZHOU NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] There have been some reports on the direct functionalization of allyl alcohols, such as the palladium-catalyzed direct oxidative alkylation of terminal allyl alcohols developed by Loh’s research group for the preparation of conjugated diene derivatives. In this method, the hydroxyl groups serve as The directing group selectively activates the carbon-hydrogen bond at the ortho position of the directing group and undergoes alkenylation (Chelation versus Non-Chelation Control in the Stereoselective Alkenyl sp2 C-H Bond Functionalization Reaction. Angew. Chem., Int. Ed. 2017, 56, 5091), However, how to realize the chemical conversion of allyl alcohol with double bonds inside, and how to realize the activation and functionalization of the carbon-hydrogen bond of the directing group are still a difficult problem.

Method used

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  • A kind of alkenylated product of allyl alcohol urethane compound and its synthetic method
  • A kind of alkenylated product of allyl alcohol urethane compound and its synthetic method
  • A kind of alkenylated product of allyl alcohol urethane compound and its synthetic method

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035]

[0036] Palladium acetate (4.5 mg, 10 mol%, 0.02 mmol), N-acetylglycine (4.7 mg, 20 mol%, 0.04 mmol), silver carbonate (165.5 mg, 3.0 eq, 0.6 mmol) was charged to an oven-dried screw cap vial and trifluoroethanol (1.0 mL). Then, the corresponding carbamate (0.2 mmol, 1.0 equiv) and the corresponding alkene (0.40 mmol, 2.0 equiv) were sequentially added to the solution. The vial was sealed under nitrogen and heated to 80°C and stirred for 16 hours. After cooling, the mixture was filtered and concentrated to give the crude product, which was directly applied to flash column chromatography (ethyl acetate / petroleum ether mixture) to give bright yellow liquid (33.3 mg, yield 56%).

[0037] The NMR spectrum peaks are as follows: 1 H NMR (CDCl 3 ):δ=7.20(d,J=16.0Hz,1H),6.05(t,J=7.5Hz,1H),5.91(d,J=16.0Hz,1H),4.73(s,2H),4.09(t ,J=7.0Hz,2H),2.85(brs,3H),2.78(brs,3H),2.22-2.27(m,2H),1.56-1.61(m,2H),1.30-1.44(m,4H), 0.85-0.89(m,6H). 13 C NMR (CDCl 3): δ=166.52, 155.31, 1...

Embodiment 2

[0039]

[0040] Palladium acetate (4.5 mg, 10 mol%, 0.02 mmol), N-acetylglycine (4.7 mg, 20 mol%, 0.04 mmol), silver carbonate (165.5 mg, 3.0 eq, 0.6 mmol) was charged to an oven-dried screw cap vial and trifluoroethanol (1.0 mL). Then, the corresponding carbamate (0.2 mmol, 1.0 equiv) and the corresponding alkene (0.40 mmol, 2.0 equiv) were sequentially added to the solution. The vial was sealed under nitrogen and heated to 80°C and stirred for 16 hours. After cooling, the mixture was filtered and concentrated to give the crude product, which was directly applied to flash column chromatography (ethyl acetate / petroleum ether mixture) to give a bright yellow liquid (33.0 mg, 45% yield).

[0041] The NMR spectrum peaks are as follows: 1 H NMR (CDCl 3 ): δ=7.22(d, J=16.0Hz, 1H), 6.06(t, J=7.6Hz, 1H), 5.92(d, J=16.0Hz, 1H), 4.73(s, 2H), 3.68(s ,3H),2.85(brs,3H),2.78(brs,3H),2.22-2.28(m,2H),1.37-1.43(m,2H),0.86(t,J=7.6Hz,3H). 13 C NMR (CDCl 3 ): δ=167.85, 156.29, 146.96, 1...

Embodiment 3

[0043]

[0044] Palladium acetate (4.5 mg, 10 mol%, 0.02 mmol), N-acetylglycine (4.7 mg, 20 mol%, 0.04 mmol), silver carbonate (165.5 mg, 3.0 eq, 0.6 mmol) was charged to an oven-dried screw cap vial and trifluoroethanol (1.0 mL). Then, the corresponding carbamate (0.2 mmol, 1.0 equiv) and the corresponding alkene (0.40 mmol, 2.0 equiv) were sequentially added to the solution. The vial was sealed under nitrogen and heated to 80°C and stirred for 16 hours. After cooling, the mixture was filtered and concentrated to give the crude product, which was directly applied to flash column chromatography (ethyl acetate / petroleum ether mixture) to give a bright yellow liquid (24.8 mg, 46% yield).

[0045] The NMR spectrum peaks are as follows: 1 H NMR (CDCl 3 ): δ=7.21(d, J=16.0Hz, 1H), 6.06(t, J=7.6Hz, 1H), 5.91(d, J=16.0Hz, 1H), 4.73(s, 2H), 4.14(q ,J=7.2Hz,2H),2.85(brs,3H),2.78(brs,3H),2.22-2.27(m,2H),1.37-1.43(m,2H),1.23(t,J=7.2Hz, 3H), 0.86(t, J=7.2Hz, 3H). 13 C NMR (CDCl ...

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Abstract

The invention discloses an alkenylation product of an allyl alcohol urethane compound and a synthesis method thereof, belonging to the field of organic synthesis. The synthesis method uses allyl alcohol or cyclohexene 3-alcohol compounds as raw materials, and utilizes palladium The catalytic system realizes the selective cleavage and alkenylation of alkenyl carbon-hydrogen bonds at the same carbon position, and effectively synthesizes allyl alcohol carbamate compounds. The synthesis method provided by the present invention realizes the selective alkenylation reaction of allyl alcohol urethane for the first time, has high synthesis efficiency, is environmentally friendly, has low production environmental protection pressure, economical and easy-to-obtain raw materials, and has a wide range of substrate applications. Both cyclic and acyclic substrates are suitable, the yield can reach 45-98%, and the application range is wide; the synthetic method provided by the invention is suitable for highly efficient chemical modification of compounds with complex structures and special biological activities, and has the advantages of It has wide application prospects and is an effective supplement to the synthesis method of natural products.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to an alkenylation product of an allyl alcohol urethane compound and a synthesis method thereof. Background technique [0002] Carbamate is a commonly used functional group in organic chemistry and can be used to protect hydroxyl groups. In recent years, carbamate has also been used as a directing group for carbon-hydrogen bond orientation / site-fixed activation and functionalization. Recently, it has been reported A cross-coupling reaction between alkenyl carbamate and electron-deficient olefin, used to prepare conjugated diene derivatives in Z, E configuration, and its carbamate can also undergo chemical transformation, such as coupling reaction (Ruthenium-catalyzed olefinic C–H alkenylation of enol-carbamates: highly stereo-selective synthesis of (Z, Z) and (Z, E)-butadienes. Chem. Commun. 2017, 53, 12926). [0003] [0004] Allyl alcohol is an important class of organic compo...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C269/06C07C271/12C07D307/12C07C271/34C07J9/00C07J69/00
CPCC07C271/12C07D307/12C07C271/34C07J9/00C07J69/00C07B2200/09C07C2601/16
Inventor 张坚钟国富孟轲轲余纯冰丁丽媛
Owner HANGZHOU NORMAL UNIVERSITY
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