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Three-membered ring preparation method without metal catalysis

A three-membered ring and compound technology, which is applied in the field of metal-free catalyzed three-membered ring preparation, can solve problems such as limitations

Pending Publication Date: 2022-08-05
SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The three-membered ring structure has always been very challenging to synthesize cyclopropane, aziridine, etc. due to the existence of ring strain
Previously, sulfonium salts could also be used to construct cyclopropane structures (RSC Adv., 2017, 7, 3741; J.Am.Chem.Soc. 2021, 143, 12992), but such sulfonium salts were limited to vinyl substitution substrate

Method used

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  • Three-membered ring preparation method without metal catalysis
  • Three-membered ring preparation method without metal catalysis
  • Three-membered ring preparation method without metal catalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0101]

[0102] First p-toluenesulfonamide (41.1mg, 0.24mmol), K 2 CO 3 (27.6 mg, 0.20 mmol) and compound R-1 (86.8 mg, 0.20 mmol) were added to the reaction tube, pumped through a vacuum line for three times, and under a nitrogen atmosphere, DCM (2.0 mL) was added, and the reaction was carried out at room temperature for 24 h. After the reaction was completed, the solvent was removed by rotary evaporation, the sample was loaded by dry method, and purified by column chromatography (petroleum ether:ethyl acetate (v / v)=19:1) to obtain the product P-1 (53.1 mg, yield 88%).

[0103] 1H NMR (400MHz, CDCl 3 )δ7.86–7.81(m,2H),7.34(d,J=8.1Hz,2H),7.32–7.22(m,2H),7.22–7.16(m,1H),7.15–7.09(m,2H) ,2.78(tt,J=7.5,4.7Hz,1H),2.65-2.56(m,3H),2.45(s,3H),2.06(d,J=4.6Hz,1H),1.88(dddd,J=13.9 ,8.8,7.4,4.9Hz,1H),1.67(dtd,J=14.1,8.0,6.4Hz,1H).

[0104] 13 C NMR (101MHz, CDCl 3 )δ144.64,140.80,135.10,129.78,128.57,128.42,128.12,126.23,39.84,34.02,33.25,33.09,21.77;

[0105] HRMS-ESI(m / z)[M+...

Embodiment 2

[0107]

[0108] First p-cyanobenzenesulfonamide (43.7mg, 0.24mmol), K 2 CO 3 (27.6 mg, 0.20 mmol) and compound R-1 (86.8 mg, 0.20 mmol) were added to the reaction tube, pumped through a vacuum line for three times, and under a nitrogen atmosphere, DCM (2.0 mL) was added, and the reaction was carried out at room temperature for 24 h. After the reaction was completed, the solvent was removed by rotary evaporation, dry method was applied, and the product was purified by column chromatography (petroleum ether:ethyl acetate (v / v)=19:1) to obtain the product P-2 (40.5 mg, yield 65%).

[0109] 1 H NMR (400MHz, CDCl 3 )δ8.09–8.03(m,2H),7.87–7.81(m,2H),7.28(td,J=7.7,7.1,1.1Hz,2H),7.23–7.17(m,1H),7.13(dd, J=7.0, 1.8Hz, 2H), 2.91 (tt, J=7.3, 4.9Hz, 1H), 2.72–2.59 (m, 3H), 2.12 (d, J=4.7Hz, 1H), 1.91 (dddd, J =13.9,8.7,7.5,5.1Hz,1H),1.73(dtd,J=14.1,7.9,6.4Hz,1H);

[0110] 13 C NMR (101MHz, CDCl 3 )δ142.59,140.38,132.96,128.68,128.68,128.41,126.42,117.38,117.29,40.52,34.84,33.08,...

Embodiment 3

[0113]

[0114] First p-methoxybenzenesulfonamide (44.9mg, 0.24mmol), K 2 CO 3 (27.6 mg, 0.20 mmol) and compound R-1 (86.8 mg, 0.20 mmol) were added to the reaction tube, pumped through a vacuum line for three times, and under a nitrogen atmosphere, DCM (2.0 mL) was added, and the reaction was carried out at room temperature for 24 h. After the reaction was completed, the solvent was removed by rotary evaporation, the sample was loaded by dry method, and purified by column chromatography (petroleum ether:ethyl acetate (v / v)=19:1) to obtain the product P-3 (43.8 mg, yield 69%).

[0115] 1 H NMR (600MHz, CDCl 3 )δ7.88(d,J=8.6Hz,2H),7.27(t,J=7.5Hz,2H),7.19(t,J=7.4Hz,1H),7.12(d,J=7.5Hz,2H) ,7.00(d,J=8.5Hz,2H),3.88(s,3H),2.75(td,J=7.4,3.7Hz,1H),2.66–2.55(m,3H),2.04(d,J=4.5 Hz,1H),1.88(dddd,J=13.8,8.8,7.3,4.9Hz,1H),1.73–1.63(m,1H);

[0116] 13 C NMR (151MHz, CDCl 3 )δ163.76,140.85,130.32,129.65,128.60,128.46,126.26,114.38,55.80,39.82,33.97,33.27,33.14;

[0117] HRMS-ESI(m...

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Abstract

The invention discloses a novel preparation method of a three-membered ring, which comprises the following step: reacting an amino derivative or an alkyl derivative containing an electron withdrawing group as a substrate with olefin thianthrene salt in an organic solvent in the presence of alkali at room temperature to obtain a three-membered ring product. The preparation method has the characteristics of mild conditions, no transition metal participation, small environmental pollution and high yield.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis methods, and specifically discloses a method for preparing a three-membered ring without metal catalysis. Background technique [0002] Three-membered ring structures such as cyclopropane and aziridine widely exist in natural products and biologically active molecules, and are a very important class of organic synthesis intermediates. The synthesis of cyclopropanes, aziridines, etc. has always been very challenging due to the existence of ring tension in the three-membered ring structure. Among them, the synthesis of aziridine, the main existing synthesis method is through the insertion reaction of aziridine analogs or precursors to alkenes, containing NH 2 The double nucleophilic substitution reaction of the vicinal position in the group molecule, and the imine group in the molecule accepts the addition reaction of the carbene analog. Currently using NH 2 There are two methods for s...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D203/24C07D203/20C07D203/18C07D203/26C07D203/08C07D203/14C07D401/06C07D223/32C07C315/04C07C253/30C07C67/343C07C45/68C07C317/44C07C255/46C07C69/753C07C49/792
CPCC07D203/24C07D203/20C07D203/18C07D203/26C07D203/08C07D203/14C07D401/06C07D223/32C07C315/04C07C253/30C07C67/343C07C45/68C07C2601/02C07C317/44C07C255/46C07C69/753C07C49/792
Inventor 舒伟刘明上
Owner SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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