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Alkenylation product of allylic alcohol carbamate compound and synthesis method thereof

A technology for allyl alcohol amine carboxylic acid and ester compounds, which is applied in the preparation of organic compounds, steroid compounds, organic chemical methods, etc., to achieve the effects of environmental friendliness, wide application range and mild reaction conditions

Active Publication Date: 2020-01-03
HANGZHOU NORMAL UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

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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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  • Alkenylation product of allylic alcohol carbamate compound and synthesis method thereof
  • Alkenylation product of allylic alcohol carbamate compound and synthesis method thereof
  • Alkenylation product of allylic alcohol carbamate compound and synthesis method thereof

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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 crude product, which was directly applied to flash column chromatography (ethyl acetate / petroleum ether mixture) to give bright yellow liquid (33.0 mg, yield 45%).

[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, 146.69,...

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 bright yellow liquid (24.8 mg, yield 46%).

[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 3 ...

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Abstract

The invention discloses an alkenylation product of allylic alcohol carbamate compound and a synthesis method thereof, and belongs to the field of organic synthesis. The synthesis method comprises thefollowing steps of taking allylic alcohol or cyclohexene 3-alcohol compound as raw material, realizing selective cutting and alkenylation of alkenyl carbon-hydrogen bond at same carbon position of thealkenyl, and effectively synthesizing allylic alcohol carbamate compound. Through the synthesis method provided by the invention, the selective olefination reaction of the allylic alcohol carbamate is realized for the first time; the method is high in synthesis efficiency, environment-friendly, small in production environment-friendly pressure, economic and easily available in raw materials, extensive in applicable range of the substrate, and suitable for both cyclic and non-cyclic substrates; the yield can reach 45-98%, and the application range is extensive. The synthesis method provided bythe invention is suitable for effectively and chemically modifying the compound with special biological activity and complex structure, has extensive application prospect and is effective supplementon the synthetic 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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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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