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-CI)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1.3-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.
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.