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有机化学
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有机化学 ›› 2011, Vol. 31 ›› Issue (04): 538-543. 上一篇    下一篇

研究论文

S-[2-(叔丁氧羰基氨基)乙基]-3-苯基丙酸硫酯类化合物脱除Boc保护基的反应研究

贾尧玲1，王洋*,1,2   

  1. (1复旦大学药学院药物化学教研室 上海 201203)
    (2中国科学院上海药物研究所新药研究国家重点实验室 上海 201203)
  • 收稿日期:2011-01-28 修回日期:2011-03-02 发布日期:2011-03-10
  • 通讯作者: 王洋 E-mail:wangyang@shmu.edu.cn

Study on the Deprotection of Boc Group of S-2-(tert- Butoxycarbonylamino)ethyl 3-Phenylpropanethioates

Jia Yaoling1 Wang Yang*,1,2   

  1. (1 Department of Medicinal Chemistry, School of Pharmacy, Fudan University, Shanghai 201203)
    (2 State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203)
  • Received:2011-01-28 Revised:2011-03-02 Published:2011-03-10
  • Contact: Yang WANG E-mail:wangyang@shmu.edu.cn

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报道了取代苯丙酸类化合物1a～1d与N-叔丁氧羰基-L-半胱氨酸甲酯(2)在双(2-氧代-3-噁唑烷基)次磷酰氯(BOP-Cl)作用下, 以79%～92%收率得到缩合产物S-[2-(叔丁氧羰基氨基)乙基]-3-苯基丙酸硫酯类化合物3a～3d|3a～3d在三氟乙酸(TFA)作用下脱除Boc保护基时, 结果不仅得到了正常的脱保护基产物4a～4d, 还生成了2-取代噻唑啉类化合物5a～5d, 研究表明5a～5d是由4a～4d分子内脱水环合而成. 通过优化三氟乙酸用量、反应温度以及反应时间等条件, 能够以较高收率分别得到4a～4d和5a～5d(收率85%～91%和86%～89%). 而S-[2-(叔丁氧羰基氨基)乙基]-3-苯基丙烯酸硫酯类化合物3e～3f由于双键结构, 在三氟乙酸作用下仅生成脱除Boc保护基产物4e～4f. 该反应的研究为2-取代噻唑啉类化合物的合成提供了一种简便有效的方法.

关键词: S-[2-(叔丁氧羰基氨基)乙基]-3-苯基丙酸硫酯, 噻唑啉, Boc保护基, 三氟乙酸

S-2-(tert-Butoxycarbonylamino)ethyl 3-phenylpropanethioates (3a～3d) were synthesized in 79%～92% yields through the esterification of substituted 3-phenylpropanoic acids (1a～1d) and methyl N-(tert-butoxycarbonyl)-L-cysteine (2) by using bis(2-oxo-3-oxazolidinyl)phosphinic chloride (BOP-Cl) as the condensation agent. The deprotection of Boc group of 3a～3d by trifluoroacetic acid (TFA) gave not only normal deprotecting products 4a～4d but also 2-substituted thiazolines 5a～5d which were obtained by intramolecular dehydration of the corresponding 4a～4d, whereas the deprotection of Boc group of S-2-(tert-butoxycarbonylamino)ethyl 3-phenylpropenethioates (3e～3f) afforded only deprotecting products 4e～4f under the same condition due to their double bond rigid structures. 4a～4d and 5a～5d could be obtained in high yields (85%～91% and 86%～89%) respectively by optimizing reaction conditions on the amount of TFA, the reaction temperature and time, which provided a facile and effective method to synthesize 2-substituted thiazolines.

Key words: S-2-(tert-butoxycarbonylamino)ethyl 3-phenylpropanethioate, thiazoline, Boc group, trifluoroacetic acid (TFA)