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高等学校化学研究 ›› 2012, Vol. 28 ›› Issue (5): 843-846 .

• Articles • 上一篇    下一篇

Flexible Synthesis of Enantiomeric and Racemic 3-Hydroxymethyl-1,2,3,4-tetrahydroisoquinolines via Bischler-Napieralski Reaction

KANG Chuan-qing1,2, DU Zhi-jun1,2, WANG Lan-lan1, CHEN Yu1, QIU Xue-peng1, GUO Hai-quan1, GAO Lian-xun1   

  1. 1. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China;
    2. Graduate School of Chinese Academy of Sciences, Beijing 100049, P. R. China
  • 收稿日期:2011-11-03 修回日期:2011-11-08 出版日期:2012-09-25 发布日期:2012-09-07
  • 通讯作者: GAO Lian-xun E-mail:lxgao@ciac.jl.cn

Flexible Synthesis of Enantiomeric and Racemic 3-Hydroxymethyl-1,2,3,4-tetrahydroisoquinolines via Bischler-Napieralski Reaction

KANG Chuan-qing1,2, DU Zhi-jun1,2, WANG Lan-lan1, CHEN Yu1, QIU Xue-peng1, GUO Hai-quan1, GAO Lian-xun1   

  1. 1. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China;
    2. Graduate School of Chinese Academy of Sciences, Beijing 100049, P. R. China
  • Received:2011-11-03 Revised:2011-11-08 Online:2012-09-25 Published:2012-09-07

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摘要： With methyl ester of N-acylated L-3-(3,4-dihydroxyphenyl)alanine(L-DOPA) as starting material, racemic derivatives of 3-hydroxymethyl-1,2,3,4-tetrahydroisoquinoline were obtained with cyclization by Bischler-Napie- ralski(BN) reaction followed by reduction of methyl ester group to hydroxymethyl, while the optical pure enantiomers were prepared by the reduction of the methyl ester group to hydroxymethyl prior to cyclization with BN reaction. Racemerization took place in the BN stage in the presence of methyl ester, an electron-withdrawing group adjacent to chiral center. Therefore, the sequence of synthetic stages of cyclization and reduction, and subsequently whether there is electron-withdrawing group or not determines the chiral optical activity of the products.

关键词: 1,2,3,4-Tetrahydroisoquinoline, Bischler-Napieralski reaction, Racemerization

Abstract: With methyl ester of N-acylated L-3-(3,4-dihydroxyphenyl)alanine(L-DOPA) as starting material, racemic derivatives of 3-hydroxymethyl-1,2,3,4-tetrahydroisoquinoline were obtained with cyclization by Bischler-Napie- ralski(BN) reaction followed by reduction of methyl ester group to hydroxymethyl, while the optical pure enantiomers were prepared by the reduction of the methyl ester group to hydroxymethyl prior to cyclization with BN reaction. Racemerization took place in the BN stage in the presence of methyl ester, an electron-withdrawing group adjacent to chiral center. Therefore, the sequence of synthetic stages of cyclization and reduction, and subsequently whether there is electron-withdrawing group or not determines the chiral optical activity of the products.

Key words: 1,2,3,4-Tetrahydroisoquinoline, Bischler-Napieralski reaction, Racemerization