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Preparation method of polysubstituted cyclobutane compound

A compound, cyclobutane technology, applied in the field of preparation of multi-substituted cyclobutane compounds, to achieve the effect of easy large-scale production, high reactivity, and rich substrate range

Active Publication Date: 2021-08-24
QINGDAO UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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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  • Preparation method of polysubstituted cyclobutane compound
  • Preparation method of polysubstituted cyclobutane compound
  • Preparation method of polysubstituted cyclobutane compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

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

[0032]

[0033] In the reaction flask, add compound 1a (100mmol), compound 2a (500mmol), Ir (ppy) 3 (1mmol), Rh 2 (OAc) 4 (5mmol), 1,2-dichloroethane (DCE, 500mL), irradiated under blue LED lamp for 12h. After the reaction was completed, the reaction solvent was removed by a rotary evaporator to obtain a crude product, which 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] In the reaction flask, add compound 1a (100mmol), compound 2b (500mmol), Ir (ppy) 3 (1mmol), Rh 2 (OOc) 4 (5mmol), 1,2-dichloroethane (DCE, 500mL), irradiated under blue LED lamp for 12h. After the reaction, the reaction solvent was removed using a rotary evaporator to obtain a crude product, which was separated by column chromatography to obtain the target product 3b with a yield of 60% (3:1d.r.).

[0041] 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, reaction equation is as follows:

[0046]

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

[0048] 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 a polysubstituted cyclobutane compound, and belongs to the technical field of organic synthesis. The method comprises the following steps: by taking an iridium photosensitizer and transition metal RhII as a mixed catalyst, carrying out [2+2] cycloaddition reaction on a diazo compound and olefin under the irradiation condition of a blue light LED lamp, so as to directly generate the polysubstituted cyclobutane compound. The method for preparing the polysubstituted cyclobutane compound by utilizing photocatalysis and transition metal catalysis of the [2+2] cycloaddition reaction of the diazo compound and the olefin has the characteristics of being scientific, reasonable, environment-friendly, simple in synthesis method, high in target compound yield, wide in substrate applicability and the like.

Description

technical field [0001] The invention discloses a preparation method of multi-substituted cyclobutane compounds belonging 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 of blue LED lamps, the [2+2] cycloaddition reaction of diazo compounds and alkenes can directly generate multi-substituted cyclobutane compounds. The synthesis method of the multi-substituted cyclobutane compound of the invention has the characteristics of scientific rationality, environmental friendliness, simple synthesis method, high yield of target compound, wide substrate applicability and the like. Background technique [0002] Visible light-induced [2+2] cycloaddition reaction is a green, efficient and environmentally friendly synthetic method for constructing cyclobutane skeletons, which has attracted the interest of chemists for a long time. Recently, Wu Lizhu (Angew.Chem.Int.Ed.2017...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/753C07C67/347C07C45/69C07C49/563B01J31/22
CPCC07C67/347C07C45/69B01J31/2295B01J31/2239B01J2231/328B01J2531/827B01J2531/822C07C2601/04C07C2601/02C07C2603/12B01J35/19B01J35/39C07C69/753C07C49/563
Inventor 吕健禚彩琪尚万送刘永军
Owner QINGDAO UNIV OF SCI & TECH
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