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Stereoselective synthesis method of tetra-substituted allyl azide

An allyl azide and stereoselective technology, applied in chemical instruments and methods, organic chemistry, metallocene, etc., can solve the problems of limited universality of substrates, cumbersome reaction steps, and low selectivity, achieving Easy operation, high yield and selectivity, fast reaction speed

Pending Publication Date: 2022-02-15
鄂尔多斯应用技术学院
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Problems solved by technology

The synthesis methods of such compounds generally have cumbersome reaction steps, some use noble metals as catalysts, and the universality of substrates is also limited, and the selectivity of the reaction is not high.

Method used

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  • Stereoselective synthesis method of tetra-substituted allyl azide
  • Stereoselective synthesis method of tetra-substituted allyl azide
  • Stereoselective synthesis method of tetra-substituted allyl azide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Synthesis of (E)-dimethoxy(3-ferrocenyl-3-azido-2-iodo-1-(4-methoxy)phenylpropenyl)phosphate

[0026] In the 25mL reaction flask, add ferrocene allenyl phosphate dimethyl ester compound (88 mg, 0.20mmol), NaN 3 (26mg, 0.40mmol), elemental iodine (61mg, 0.24 mmol). Then add 2.0ml CH 3 CN, stirred at room temperature and detected by TLC that the reaction was complete, separated by column chromatography, using petroleum ether: ethyl acetate (V:V) = 3:1 as the eluent, purified to obtain a yellow solid with a yield of 84%. Its NMR data are as follows:

[0027]

[0028] The NMR characterization data of the synthesized new compound: 1 H NMR(500MHz,DMSO)δ6.93(d,J=21.0Hz,4H),6.91(s,1H),4.40(s,1H),4.35(s,1H),4.26(s,5H),4.22 (s,2H),3.77(s,3H),3.74–3.58(m,6H). 31 P NMR (202MHz, DMSO) δ10.6. 13 C{ 1 H}NMR (125 MHz, DMSO) δ159.4, 140.5, 139.2, 135.5, 135.4, 134.9 (d, J pc =6.9Hz), 130.3(d,J pc =68.0Hz), 114.3, 87.6, 69.5, 69.0, 67.8 (d, J pc =13.7Hz), 67.5,65.3(d,J pc =4...

Embodiment 2

[0030] Synthesis of (E)-dimethoxy(3-ferrocenyl-3-azido-2-iodo-1-phenylpropenyl)phosphate

[0031] Add ferrocene allenyl phosphate dimethyl ester compound (81 mg, 0.20mmol), NaN 3 (26mg, 0.40mmol), elemental iodine (61mg, 0.24 mmol). Then add 2.0ml CH 3 CN, stirred at room temperature and detected by TLC that the reaction was complete, separated by column chromatography, using petroleum ether: ethyl acetate (V:V) = 3:1 as the eluent, purified to obtain a yellow solid with a yield of 72%. Its NMR data are as follows:

[0032]

[0033] 1 H NMR (500MHz, CDCl 3 )δ7.36(s,3H),7.14(s,1H),7.02(s,1H), 6.78(d,J=2.3Hz,1H),4.49(s,1H),4.42(d,J=0.8 Hz,1H),4.30(s,5H),4.23–4.18(m,2H),3.79(d,J=11.3Hz,3H),3.70(d,J=11.2Hz, 3H). 31 P NMR (202MHz, CDCl 3 )δ10.0. 13 C{ 1 H}NMR (125MHz, CDCl 3 )δ142.6(d,J pc =7.0Hz), 140.2, 138.9, 135.5, 135.3, 128.44, 128.3 (d, J pc =1.9Hz), 87.5, 69.3, 68.6, 67.7 (d, J pc =13.0Hz), 67.4, 65.4 (d, J pc =5.2Hz), 53.1(dd, J pc =7.5,6.3Hz).

Embodiment 3

[0035] Synthesis of (E)-dimethoxy(3-ferrocenyl-3-azido-2-iodo-1-methylpropenyl)phosphate

[0036] Add alkyl allenyl phosphate compound (69.2mg, 0.20mmol), NaN 3 (26mg, 0.40mmol), elemental iodine (61mg, 0.24mmol). Then add 2.0ml CH 3 CN, stirred at room temperature and detected by TLC that the reaction was complete, separated by column chromatography, using petroleum ether: ethyl acetate (V:V) = 3:1 as the eluent, purified to obtain a yellow solid with a yield of 62%. Its NMR data are as follows:

[0037]

[0038] 1 H NMR (500MHz, DMSO) δ6.79(s,1H),4.35(s,1H),4.22(s,5H),4.20(s,2H),4.17(s,1H),3.77(t,J= 12.4Hz,6H),2.02(d,J=11.9Hz,3H). 31 P NMR (202MHz, DMSO) δ13.9. 13 C{ 1 H}NMR(125MHz, DMSO)δ132.8(dd,J pc =88.9,71.1Hz),87.8,69.8,69.4,68.9,67.7(d, J pc =18.4Hz), 67.4, 65.6(d, J pc =5.8Hz), 53.2(d, J pc =5.0Hz), 28.4(d, J pc= 8.9Hz).

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Abstract

The invention discloses a stereoselective synthesis method of a tetra-substituted allyl azide compound. The method comprises the steps that ferrocene allene dimethyl phosphate reacts with an azide nucleophilic reagent NaN3 and an iodine elementary substance under the condition of room temperature, and a series of tetra-substituted allyl azide compounds containing different substituent groups are obtained by dissolving through an organic solvent. The method has the characteristics of high reaction efficiency, good economical efficiency, high synthesis rate and simplicity and convenience in operation.

Description

technical field [0001] The invention belongs to the technical field of tetrasubstituted allyl azide compounds, in particular to a stereoselective synthesis method of tetrasubstituted allyl azide compounds. Background technique [0002] Tetrasubstituted allyl azides are important intermediates in organic synthesis. Due to the high activity of the azido group itself, it is an attractive structural unit in many natural products, medicines and organic functional materials. In addition, azide compounds can also be used to synthesize nitrogen-containing heterocyclic compounds, such as aziridines, triazoles, pyrazines, pyrroles, and other heterocyclic compounds. At the same time, it is reduced to amino and cyano, and loses nitrogen at high temperature to obtain azide base. The synthesis methods of such compounds generally have cumbersome reaction steps, some use noble metals as catalysts, and the universality of substrates is also limited, and the selectivity of the reaction is n...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F17/02
CPCC07F17/02
Inventor 郭乐高艳鹏李英杰吴永丽王悦李威龙
Owner 鄂尔多斯应用技术学院
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