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A kind of preparation method of polysubstituted cyclobutane compound

A compound, cyclobutane technology, which is applied in the field of preparation of polysubstituted cyclobutane compounds, and achieves the effects of rich substrate range, easy large-scale production and high reactivity

Active Publication Date: 2022-06-21
QINGDAO UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the [2+2] cycloaddition reactions of diazo compounds with different types of alkenes induced by visible light have not been reported so far. The reason may be that diazo compounds are prone to Wolff rearrangement reactions to form cyclobutanone. Compounds

Method used

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  • A kind of preparation method of polysubstituted cyclobutane compound
  • A kind of preparation method of polysubstituted cyclobutane compound
  • A kind of preparation method of polysubstituted cyclobutane compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] The preparation of cyclobutane compound 3a, the reaction equation is as follows:

[0032]

[0033] Add compound 1a (100 mmol), compound 2a (500 mmol), Ir(ppy) to the reaction flask 3 (1mmol), Rh 2 (OAc) 4 (5 mmol), 1,2-dichloroethane (DCE, 500 mL), irradiated under a blue LED light for 12 h. After the reaction, the reaction solvent was removed using a rotary evaporator to obtain a crude product. The crude product was separated by column chromatography to obtain the target product 3a with a yield of 80%.

[0034] 3a NMR data:

[0035] 1 H NMR (500MHz, CDCl 3 ):δ7.30(d,J=4.0Hz,4H),7.18-7.09(m,7H),6.96(d,J=7.0Hz,2H),6.88(d,J=4.0Hz,2H),4.58 (d, J=10.5Hz, 1H), 4.13-4.03 (m, 2H), 3.51 (q, J=10.0Hz, 1H), 3.36-3.32 (m, 1H), 2.69 (t, J=11.0Hz, 1H), 1.18(t, J=7.0Hz, 3H)ppm.

[0036] 13 C NMR (125MHz, CDCl 3 ):δ173.9,150.7,141.5,138.6,128.8,128.6,128.4,127.7,126.7,126.3,126.1,125.9,60.6,54.0,52.7,39.8,34.6,14.2ppm.

Embodiment 2

[0038] The preparation of cyclobutane compound 3b, the reaction equation is as follows:

[0039]

[0040] Add compound 1a (100 mmol), compound 2b (500 mmol), Ir(ppy) to the reaction flask 3 (1mmol), Rh 2 (OOc) 4 (5 mmol), 1,2-dichloroethane (DCE, 500 mL), irradiated under a blue LED light for 12 h. After the reaction, the reaction solvent was removed using a rotary evaporator to obtain a crude product. The crude product was separated by column chromatography to obtain the target product 3b with a yield of 60% (3:1 d.r.).

[0041] The 3b NMR data are as follows:

[0042] 1 H NMR (500MHz, CDCl 3 ): δ7.34-7.23(m, 5H), 4.22(d, J=10.5Hz, 1H), 4.18-4.13(m, 2H), 3.78(s, 3H), 3.44(q, J=9.5Hz, 1H), 2.72(t, J=10.5Hz, 1H), 2.04(dd, J=8.5, 11.0Hz, 1H), 1.25(t, J=7.5Hz, 3H), 1.05(s, 3H)ppm.

[0043] 13 C NMR (125MHz, CDCl 3 ): δ176.8,173.8,137.9,128.2,127.4,126.6,60.7,52.1,48.0,44.2,36.0,32.1,18.6,14.2ppm.

Embodiment 3

[0045] The preparation of cyclobutane compound 3c, the reaction equation is as follows:

[0046]

[0047] Add compound 1a (100 mmol), compound 2c (500 mmol), Ir(ppy) to the reaction flask 3 (1mmol), Rh 2 (OAc) 4 (5 mmol), 1,2-dichloroethane (DCE, 500 mL), irradiated under a blue LED light for 12 h. After the reaction, use a rotary evaporator to remove the reaction solvent to obtain a crude product. The crude product is separated by column chromatography to obtain the target product 3c with a yield of 85% (10:1 d.r.).

[0048] The 3c NMR data are as follows:

[0049] 1 H NMR (500MHz, CDCl 3 ): δ7.31-7.19(m, 10H), 4.23-4.16(m, 2H), 3.69(t, J=10.0Hz, 1H), 3.20(t, J=10.0Hz, 1H), 2.86(t, J=9.5Hz, 1H), 2.25(q, J=9.5Hz, 1H), 1.28(t, J=7.0Hz, 3H), 1.01-0.95(m, 1H), 0.51-0.43(m, 2H), 0.24-0.18(m,2H)ppm.

[0050] 13 C NMR (125MHz, CDCl 3 ): δ171.6,140.2,139.9,126.1,124.8,124.3,124.2,124.2,58.2,47.3,45.5,44.9,43.9,11.9,11.7ppm.

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Abstract

The invention discloses a method for preparing multi-substituted cyclobutane compounds, which belongs to the technical field of organic synthesis. The method is: with iridium photosensitizer and transition metal Rh II In order to mix catalysts, under the irradiation conditions of blue LED lamps, the [2+2] cycloaddition reaction of diazo compounds and alkenes can directly generate multi-substituted cyclobutane compounds. The method for preparing multi-substituted cyclobutane compounds by using photocatalysis and transition metal catalyzed [2+2] cycloaddition reaction of diazonium compounds and alkenes in the present invention has the advantages of scientific rationality, environment-friendly, simple synthesis method and objective It has the characteristics of high compound yield and wide substrate applicability.

Description

technical field [0001] The invention discloses a preparation method of a polysubstituted cyclobutane compound belonging to the technical field of organic synthesis. The method is: using iridium photosensitizer and transition metal Rh II As a mixed catalyst, under the irradiation of a blue LED lamp, a [2+2] cycloaddition reaction between diazo compounds and alkenes can directly generate polysubstituted cyclobutane compounds. The method for synthesizing the polysubstituted cyclobutane compound of the present invention has the characteristics of scientific rationality, environmental friendliness, simple synthesis method, high yield of target compounds, wide applicability of substrates, and the like. Background technique [0002] Visible light-induced [2+2] cycloaddition is a green, efficient, and environmentally friendly synthetic method for building cyclobutane skeletons, which has always attracted the interest of chemists. Recently, Wu Lizhu (Angew.Chem.Int.Ed. 2017, 56, 15...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C69/753C07C67/347C07C45/69C07C49/563B01J31/22
CPCC07C67/347C07C45/69B01J31/2295B01J31/2239B01J35/0006B01J35/004B01J2231/328B01J2531/827B01J2531/822C07C2601/04C07C2601/02C07C2603/12C07C69/753C07C49/563
Inventor 吕健禚彩琪尚万送刘永军
Owner QINGDAO UNIV OF SCI & TECH
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