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A method for efficiently synthesizing (1r,2s)-1,2-dihydronaphthalene derivatives

A technology for dihydronaphthalene derivatives and compounds, which is applied in the fields of chemical synthesis and chemistry, can solve the problems of harsh reaction conditions, inability to prepare cis-diol compounds, and long reaction time, and achieves easy reaction, low cost and high efficiency. Effect

Inactive Publication Date: 2020-12-15
YUNNAN MINZU UNIV
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

[0006] In 2007, the research group of Augusto R. Rodrigues successfully prepared the cis (1 S , 2 R ) -1, 2, 3,4-tetrahydronaphthalene-1,2-diol ( Adv. Synth. Catal. 2007, 349 , 925– 932.), and achieved good results, but the reaction conditions are relatively harsh, the reaction time is longer, and there will be trans-diol formation
[0008] In 2015, Serdar Gultekin's research group reported ( ± )-1, 2, the synthetic method of 3,4-tetrahydronaphthalene-1,2-diol ( RSC Adv ., 2015, 5 , 20751–20755.), although this method is simple (as shown in the following formula), it cannot prepare optically pure cis-diol compounds

Method used

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  • A method for efficiently synthesizing (1r,2s)-1,2-dihydronaphthalene derivatives
  • A method for efficiently synthesizing (1r,2s)-1,2-dihydronaphthalene derivatives
  • A method for efficiently synthesizing (1r,2s)-1,2-dihydronaphthalene derivatives

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Experimental program
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Embodiment 1

[0042] Tert -butyl((1 R ,2 S )-2-(((( E )-benzylidene)amino)oxy)-1,2-dihydronaphthalen-1-yl)carbamate was synthesized: 2.3mgPd(AcO) 2 and 8.2mg ( R )-Difluorphos was stirred in 1mL 1,2-dichloroethane for 30min, followed by the addition of 7.3mgZn(OTf) 2Stir for 10 min, then add 50 mg 4 Å molecular sieves, 48.6 mg of azabenzonorbornene protected by Boc and 1 ml of 1,2-dichloroethane and stir for 10 min, then add 72.6 mg of benzaldoxime, then plug the stopper and stop the reaction The glove box was taken out, and the reaction was stirred in an oil bath at 90°C. After the reaction was monitored by TLC, a white solid was obtained by silica gel column chromatography after concentration, with a yield of 78% and an ee value of 94%.

[0043] White solid, 78% yield, 94% ee .mp 126-128 o C. [α] D 20 = +358.3 (c =0.40, CH 2 Cl 2 ). 1 H NMR (400 MHz, CDCl 3 ): δ 7.99 (s, 1H), 7.48-7.45 (m,2H),7.39-7.24 (m, 6H), 7.16-7.14 (m, 1H), 6.68 (d, J =10.0 Hz, 1H), 6.21 (dd, J =4.0...

Embodiment 2

[0045] Tert -butyl((1 R ,2 S )-2-(((( E )-4-methylbenzylidene)amino)oxy)-1,2-dihydronaphthalen-1-yl)carbamate was synthesized: 2.3mgPd(AcO) 2 and 8.2mg ( R )-Difluorphos was stirred in 1mL 1,2-dichloroethane for 30min, followed by the addition of 7.3mgZn(OTf) 2 Stir for 10min, then add 50mg of 4 Å molecular sieves, 48.6mg of azabenzonorbornene protected by Boc and 1ml of 1,2-dichloroethane and stir for 10min, then add 81.1mg of p-tolualdehyde oxime, then stopper The stopper took the reaction out of the glove box, placed the reaction in an oil bath at 90°C and stirred it. After the reaction was monitored by TLC, it was concentrated and subjected to silica gel column chromatography to obtain a white solid with a yield of 55% and an ee value of 94%.

[0046] White solid, 55% yield, 94% ee .mp 103-105 o C. [α] D 20 = +332.8 (c =0.86, CH 2 Cl 2 ). 1 H NMR (400 MHz, CDCl 3 ): δ 8.00 (s, 1H), 7.40 (t, J =8.0 Hz,3H),7.30-7.26 (m, 2H), 7.17 (t, J =4.0 Hz, 3H), 6.71 (d,...

Embodiment 3

[0048] Tert -butyl((1 R ,2 S )-2-(((( E )-3-methylbenzylidene)amino)oxy)-1,2-dihydronaphthalen-1-yl)carbamate synthesis: 2.3mg Pd(AcO) 2 and 8.2mg ( R )-Difluorphos was stirred in 1mL 1,2-dichloroethane for 30min, followed by the addition of 7.3mg Zn(OTf) 2 Stir for 10min, then add 50mg 4 Å molecular sieves, 48.6mg azabenzonorbornene protected by Boc and 1ml 1,2-dichloroethane and stir for 10min, then add 81.1mg m-tolualdehyde oxime, then stopper The stopper took the reaction out of the glove box, and placed the reaction in an oil bath at 90°C to stir. After the reaction was monitored by TLC, it was concentrated and passed through a silica gel column to obtain a white solid with a yield of 72% and an ee value of 94%.

[0049] White solid, 79% yield, 94% ee .mp 74-76 o C. [α] D 20 = +366.7 (c = 0.32,CH 2 Cl 2 ). 1 H NMR (400 MHz, CDCl 3 ): δ 8.30 (s, 1H), 7.58 (d, J =7.6 Hz,1H), 7.42(d, J =5.2 Hz, 1H), 7.33-7.25 (m, 3H), 7.18 (dd, J =7.2Hz, J =10.8 Hz, 3H), 6...

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Abstract

The invention discloses a method for efficiently synthesizing a (1R,2S)-1,2-dialin derivative. The method is characterized by carrying out asymmetric cis-form ring opening on nitrogen / oxygen benzene and norbornene by taking an oximes compound as a nucleophilic reagent in an organic solvent system and under an inertial atmosphere, thus obtaining a target object-the (1R,2S)-1,2-dialin derivative, wherein a reaction formula of the (1R,2S)-1,2-dialin derivative is as shown in the description. According to the method disclosed by the invention, efficient synthesis of the (1R,2S)-1,2-dialin-1,2-diamine derivative through one-step simple reaction by taking the simple oximes compound, the nitrogen / oxygen benzene and norbornene compounds as raw materials is realized for the first time, wherein a hydroxyl group (-OH) or amino group (-NH2) is used as a substituent group.

Description

technical field [0001] The invention belongs to the technical field of chemistry, and further belongs to the technical field of chemical synthesis, in particular to a highly efficient synthesis (1 R ,2 S )-1,2-dihydronaphthalene derivatives. Background technique [0002] The structural units of dihydronaphthalene and tetralin are the backbone parts of many natural products and bioactive molecules, and they are also widely used synthetic intermediates in the fields of energy, chemical industry, and pharmaceuticals. So far, some literatures have reported about (1 R , 2 S )-1-amino-1,2,3,4-tetralin-2-ol and (1 R , 2 S )-1, 2, 3, 4-tetrahydronaphthalene-1,2-diol synthetic method. Among them, M. K. Lakshman research group reported in 1998 (1 R , 2 S )-1-amino-1,2,3,4-tetralin-2-ol synthesis ( Synthesis , 1998, 1352-1356.), the experimental steps of this method are relatively cumbersome (as shown in the following formula), the final yield is not ideal, and more dangerous ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C249/12C07C251/58C07C269/06C07C271/24C07D317/70
CPCC07C249/12C07C269/06C07D317/70C07C2602/10C07C251/58C07C271/24
Inventor 樊瑞峰周永云陈景超樊保敏孙蔚青曾广智尹俊林林成源沈国礼
Owner YUNNAN MINZU UNIV
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