反应详情
EQUATION
反应方程式
REACTANTS
反应物
PRODUCTS
生成物
AUXILIARIES
试剂、催化剂与溶剂
CONDITIONS
反应条件
- 温度
- 0 °C
PROCEDURE
实验过程
O-allyl L-seryl glycine methyl ester trifluoroacetate 20 (4.42 g, 13.4 mmol) was dissolved in CH2Cl2 (40 mL) and N-tert-butoxycarbonyl O-allyl L-seryl α,α-dimethylglycyl L-valine 16 (5.75 g, 13.4 mmol) added. N,N-diisopropylethyl amine (1.73 g, 13.4 mmol) and HOBt hydrate (2.05 g, 13.4 mmol) were added and the solution cooled to 0° C. EDC hydrochloride (2.82 g, 14.7 mmol) was added in small portions together with 10 mL CH2Cl2. The reaction mixture was stirred for 1 h 30 min at 0° C. after which the icebath was removed and the mixture stirred for an additional 26 hours. The solution was diluted by addition of CH2Cl2 (60 mL) and washed with 2 M aqueous H2SO4 (3×90 mL), 7.5% (w/w) aqueous K2CO3 (3×90 mL) and saturated brine (90 mL). The volume was increased by addition of CH2Cl2, the solution dried with anhydrous MgSO4 and the solvent evaporated affording a slightly orange solid (6.14 g, 73%); δH (300 MHz; d6-DMSO) 8.25 (1H, t, J 6, NH(Gly)), 8.14 (1H, s, NH(Aib)), 7.88 (1H, d, J 8, NH(Ser(All))), 7.14 (1H, d, J 8, NH(Val)), 6.84 (1H, d, J 7, NH (Ser(All)1)), 5.92-5.74 (2H, m, CH═CH2), 5.28-5.11 (4H, m, CH═CH2), 4.50 (1H, m, CαH(Ser(All)2)), 4.17-4.09 (2H, m, CαH(Ser(All)1)/CαH(Val)), 3.95 (4H, m, CH2CH═CH2), 3.85 (2H, d, J 6, CαH2(Gly)), 3.61 (3H, s, OCH3), 3.58-3.46 (4H, m, CH2), 2.06-1.95 (1H, m, CH(CH3)2), 1.38 (9H, s, (CH3)3), 1.35 (3H, s, CH3(Aib)), 1.34 (3H, s, CH3(Aib)), 0.83 (3H, d, J 7, CH3(Val)), 0.78 (3H, d, J 7, CH3(Val)); δC (75 MHz; d6-DMSO) 173.9, 170.7, 169.9, 169.8, 169.7, 155.3, 134.8, 116.4, 116.3, 78.4, 71.0, 69.4, 58.2, 56.2, 54.8, 54.5, 52.5, 51.6, 40.6, 30.0, 28.0, 24.9, 24.7, 19.0, 17.8; m/z 650.3366 ([M+Na]+; C29H49N5O10Na requires 650.3377)
WORKUP
后处理
- customwas removed
- stirringthe mixture stirred for an additional 26 hours
- additionThe solution was diluted by addition of CH2Cl2 (60 mL)
- washwashed with 2 M aqueous H2SO4 (3×90 mL), 7.5% (w/w) aqueous K2CO3 (3×90 mL) and saturated brine (90 mL)
- temperatureThe volume was increased by addition of CH2Cl2
- dry with materialthe solution dried with anhydrous MgSO4
- customthe solvent evaporated