BOC-L-半胱氨酸甲酯

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of 1-bromomethyl-4-nitro-benzene (2.15 g, 9.95 mmol), cesium carbonate (6.49 g, 19.9 mmol) and 2-tert-butoxycarbonylamino-3-mercapto-propionic acid methyl ester (2.46 g, 10.5 mmol) in DMF (25 mL) was stirred at room temperature. Upon completion of the reaction (TLC control: 30% ethyl acetate in heptane), the reaction mixture was quenched with water (50 mL) and extracted with diethyl ether (3×50 mL). The combined extract was washed sequentially with water and brine, dried over anhydrous MgSO4, filtered and concentrated in vacuo. Purification by flash chromatography (SiO2; 30% ethyl acetate in heptane as eluent) yielded the thioether as an off-white solid. the reaction mixture was quenched with water (50 mL) extracted with diethyl ether (3×50 mL) The combined extract was washed sequentially with water and brine dried over anhydrous MgSO4 filtered concentrated in vacuo Purification by flash chromatography (SiO2; 30% ethyl acetate in heptane as eluent)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 2-tert-Butoxycarbonylamino-3-{2-[3-(2-cyclopentanecarbonyl-4-methyl-phenyl)-ureido]thiazol-5-ylsulfanyl}-propionic acid methyl ester (196 mg, 35%) was prepared from 1-(5-bromo-thiazol-2-yl)-3-(2-cyclo pentanecarbonyl-4-methyl-phenyl)-urea (408 mg, 1 mmol) and 2-tert-butoxycarbonylamino-3-mercapto-propionic acid methyl ester (470 mg, 2 mmol) following the general procedure Q.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 2-tert-Butoxycarbonylamino-3-{2-[3-(2-cyclopentanecarbonyl-4-methyl-phenyl)-ureido]thiazol-5-ylsulfanyl}-propionic acid methyl ester (196 mg, 35%) was prepared from 1-(5-bromo-thiazol-2-yl)-3-(2-cyclopentanecarbonyl-4-methyl-phenyl)-urea (408 mg, 1 mmol) and 2-tert-butoxycarbonylamino-3-mercapto-propionic acid methyl ester (470 mg, 2 mmol) following the general procedure Q.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 2-tert-Butoxycarbonylamino-3-{2-[3-(2-cyclopentanecarbonyl-4-methyl-phenyl)-ureido]thiazol-5-ylsulfanyl}-propionic acid methyl ester (196 mg, 35%) was prepared from 1-(5-bromo-thiazol-2-yl)-3-(2-cyclopentanecarbonyl-4-methyl-phenyl)-urea (408 mg, 1 mmol) and 2-tert-butoxycarbonylamino-3-mercapto-propionic acid methyl ester (470 mg, 2 mmol) following the general procedure Q.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 2-tert-Butoxycarbonylamino-3-{2-[3-(2-cyclopentanecarbonyl-4-methyl-phenyl)-ureido]thiazol-5-ylsulfanyl)-propionic acid methyl ester (196 mg, 35%) was prepared from 1-(5-bromo-thiazol-2-yl)-3-(2-cyclopentanecarbonyl-4-methyl-phenyl)-urea (408 mg, 1 mmol) and 2-tert-butoxycarbonylamino-3-mercapto-propionic acid methyl ester (470 mg, 2 mmol) following the general procedure Q.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 2-tert-Butoxycarbonylamino-3-{2-[3-(2-cyclopentanecarbonyl-4-methyl-phenyl)-ureido]thiazol-5-ylsulfanyl)-propionic acid methyl ester (196 mg, 35%) was prepared from 1-(5-bromo-thiazol-2-yl)-3-(2-cyclopentanecarbonyl-4-methyl-phenyl)-urea (408 mg, 1 mmol) and 2-tert-butoxycarbonylamino-3-mercapto-propionic acid methyl ester (470 mg, 2 mmol) following the general procedure Q.

实验步骤: 投料: 取25ml单口瓶，加入C4X-144720-SM1（0.25g 1eq）和乙腈（5ml），室温下分别加入三乙胺（0.44ml 3eq）和溴丙醇（0.12ml 1.3eq），添加完毕后，反应液升至60℃下搅拌反应1h。 TLC（PE：EA=2:1，磷钼酸显色），原料反应完全，有新点生成 后处理：反应液减压浓缩后拌样，经硅胶柱层析法分离纯化（PE：EA=6：1，得到无色油状物），HNMR（144720-s1-gz），结构正确，因原料构型不对，故=正确原料到才投

实验步骤: 纯化: 纯化：柱层析 固定相：硅胶300-400目 洗脱剂：PE；PE:EA=20:1；PE:EA=15：1； 流份监测TLC（PE：EA=5:1） 得到纯品 methyl (tert-butoxycarbonyl)-D-cysteinate g；白色油状液。 HNMR：CORRECT\n后处理: 后处理：把体系中的DMF溶剂旋干后，用EA-水萃取，收集有机相，用饱和食盐水洗涤有机相，再用无水硫酸铵干燥。旋蒸，得到粗品 methyl S-(2-(tert-butoxy)-2-oxoethyl)-N-(tert-butoxycarbonyl)-D-cysteinate。 \n反应监测: TLC（PE:EA=5:1）：原料点消失，反应完全。产物点Rf值大约在0.4，茚三酮显色剂。\n开反应: 向100mL单口瓶中加入1.5g methyl (tert-butoxycarbonyl)-D-cysteinate，10mL DMF，室温下搅拌2mins至溶解；再加入2.0eq DIPEA 2.22mL，最后加入1.5eq tert-butyl 2-bromoacetate 1.39mL，于室温下反应4h。

实验步骤: 纯化: 纯化：柱层析 固定相：硅胶300-400目 洗脱剂：PE；PE:EA=10:1； 流份监测：TLC（PE:EA=3:1）、茚三酮显色剂。 得到纯品 methyl (tert-butoxycarbonyl)-D-cysteinate；棕色油状液 1.5g HNMR：CORRECT \n后处理: 后处理：把体系中的DCM溶剂旋干，得到粗品methyl (tert-butoxycarbonyl)-D-cysteinate。\n反应监测: 反应监测：TLC（PE：EA=3:1）、茚三酮显色剂。：原料点不存在，反应完成。 LCMS：（M-1）334\n开反应: 向100mL单口瓶中加入1.31g methyl D-cysteinate hydrochloride，25mL DCM，室温下搅拌5mins至溶解；再加入1.1eq TEA 1.17mL；最后加入1.1eq di-tert-butyl dicarbonate 1.93mL，于室温下反应6h。

实验步骤: 04-04 16:48: 向250mL单口瓶中加入7.45g methyl (tert-butoxycarbonyl)-D-cysteinate，60mL DMF，室温下搅拌2mins至溶解；再加入2.0eq DIPEA 11.03mL，最后加入1.5eq tert-butyl 2-bromoacetate 6.92mL，于室温下反应4h。 后处理：把体系中的DMF溶剂旋干后，用EA-水萃取，收集有机相，用饱和食盐水洗涤有机相，再用无水硫酸铵干燥。旋蒸，得到粗品 methyl S-(2-(tert-butoxy)-2-oxoethyl)-N-(tert-butoxycarbonyl)-D-cysteinate。 纯化：柱层析 固定相：硅胶300-400目 洗脱剂：PE；PE:EA=20:1；PE:EA=10：1； 流份监测TLC（PE：EA=5:1） 得到纯品 methyl (tert-butoxycarbonyl)-D-cysteinate 7.75g；白色油状液。 HNMR：CORRECT

实验步骤: 03-24 17:15: 向250mL单口瓶中加入5.0g methyl D-cysteinate hydrochloride，90mL DCM，室温下搅拌5mins至溶解；再加入1.1eq TEA 3.24g；最后加入1.1eq di-tert-butyl dicarbonate 7.36mL，于室温下反应6h。 反应监测：（PE：EA=5:1） 后处理：把体系中的DCM溶剂旋干，得到粗品methyl (tert-butoxycarbonyl)-D-cysteinate。 纯化：柱层析 固定相：硅胶300-400目 洗脱剂：PE；PE:EA=5:1；PE:EA=3：1；PE:EA=1:1 流份监测：TLC（PE:EA=1:1） 得到纯品 methyl (tert-butoxycarbonyl)-D-cysteinate；棕色油状液 7.45g HNMR：CORRECT