(1S)-(-)-10-巯基异冰片的制备
发布日期:2020/10/26 15:27:23
背景及概述[1]
(1S)-(-)-10-巯基异冰片是一种樟脑衍生物。有文献报道其可由可商购的(+)-10-樟脑磺酰氯为原料,先制备(1S)-10-巯基樟脑,然后还原羰基得到(1S)-(-)-10-巯基异冰片。
制备[1]
步骤一、
在室温下,向可商购的(+)-10-樟脑磺酰氯(S19)(6.00g)在H2O-二恶烷(1:4、120mL)中的溶液中添加PPh3(18.8g)。回流2小时后,将混合物用H2O稀释,并用戊烷萃取(3次)。将有机层用H2O(4次)和盐水洗涤。有机层经MgSO4干燥并蒸发。残余物用柱色谱法纯化(硅胶60N,仅己烷至AcOEt-己烷=1∶4),得到(1S)-10-巯基樟脑(2o)(3.25g,74%),为无色晶体。[α]D25=+2.22(c=1.01,CHCl3).mp66°C(Hexane).1H-NMR(400MHz,CDCl3):δ2.87(dd,J=13.7,6.8Hz,1H),2.41-2.32(m,1H),2.37(dd,J=13.9,10.2,1H),2.08(t,J=3.9Hz,1H),2.04-1.84(m,4H),1.75-1.67(m,1H),1.44-1.36(m,1H),1.02(s,3H),0.91(s,3H).13C-NMR(100MHz,CDCl3):δ217.7,60.6,47.8,43.7,43.2,27.0,26.6,21.3,20.3,19.8.IR(neat,cm-1):2987,2949,2565,1734,1412,1375.MSm/z:184(M+,100%).HRMS(EI):Calcd.for C10H16OS 184.0922 (M+),found:184.0948.
步骤二、
在0℃下,向(1S)-10-巯基樟脑(2o)(2.00g)在MeOH(36.2mL)中的溶液中缓慢加入NaBH4(821mg)。将混合物在相同温度下搅拌1.5小时。将混合物用NH4Cl稀释并用AcOEt萃取(3次)。有机层用盐水洗涤,经MgSO4干燥,并蒸发。残余物用柱色谱法纯化(硅胶60N,AcOEt-己烷=1∶32至1∶16),得到(1S)-(-)-10-巯基异冰片1o(1.38g,69%),为无色晶体。[α]D25=–44.6(c=0.889,CHCl3).mp72-73°C(Hexane).1H-NMR(400MHz,CDCl3):δ3.98(quint,J=3.4Hz,1H),2.80(dd,J=12.6,9.7Hz,1H),2.56(dd,J=13.0,5.3Hz,1H),2.10(brs,1H),1.82-1.63(m,4H),1.45(td,J=12.6,4.3Hz,1H),1.32-1.24(m,2H),1.10-1.01(m,1H),1.05(s,3H),0.83(s,3H).13C-NMR(100MHz,CDCl3):δ76.5,52.9,47.5,45.7,39.5,30.3,26.8,23.7,20.6,19.9.IR(neat,cm-1):3465,2951,2879,2566,1068,1030.MSm/z:168([M-H2O]+),108(100%).HRMS(EI):Calcd.for C10H16S168.0973([M-H2O]+),found:168.1011.0
参考文献
[1] Yusuke, Sasano, Naoki,等. 2-Azaadamantane N-oxyl (AZADO)/Cu Catalysis Enables Chemoselective Aerobic Oxidation of Alcohols Containing Electron-Rich Divalent Sulfur Functionalities.[J]. Organic Letters, 2018.
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