(S)-tert-butyl 2-(2-(tert-butoxycarbonylamino)-3-hydroxy-3,3-diphenylpropoxy)acetate | 885321-47-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-tert-butyl 2-(2-(tert-butoxycarbonylamino)-3-hydroxy-3,3-diphenylpropoxy)acetate
• CAS: 885321-47-1
• 化学式: C₂₆H₃₅NO₆
• 分子量: 457.567
• InChiKey: UHYFEQODZXPZTP-NRFANRHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.17
• 重原子数：
  33.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  94.09
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (S)-tert-butyl 2-(2-(tert-butoxycarbonylamino)-3-hydroxy-3,3-diphenylpropoxy)acetate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以91%的产率得到Carbamic acid,[(1S)-2-hydroxy-1-[(2-hydroxyethoxy)methyl]-2,2-diphenylethyl]-,1,1-dimethylethyl ester
  参考文献：
  名称：

  Synthesis of chiral C/N-functionalized morpholine alcohols: study of their catalytic ability as ligand in asymmetric diethylzinc addition to aldehyde

  摘要：

  A broad variety of chiral C/N-functionalized morpholine alcohols sharing a common structural motif in the 3-(hydroxy-methyl)morpholine 6 were prepared froin criantiomerically pure serine for the purpose of studying their catalytic ligand properties. The asymmetric addition of diethylzinc to benzaldehyde in the presence of 10 mol % of chiral C/N-functionalized morpholine alcohols gave 1-phenyl-1-propanol in 59-81% yield with 10-30% ee. The addition of 10 mol % of n-butyl lithium to the reaction mixture resulted in a significant enhancement of the stereoselectivity in the case of ligands bearing the two geminal phenyl substituents on the backbone. In the presence of n-butyl lithium and using (S)-3-(hydroxydiphcnylmethyl)morpholine (S)-19 as the chiral promoter, (S)-1-phenyl-1 -propanol was obtained in 81% yield with 76% ee. The geminal diphenyl-class of morpholine ligands was examined for the diethylzinc addition to four different aldehydes in the presence of n-butyl lithium. (S)-N-Benzyl-3-(hydroxydiphenymethyl)morpholine (S)-27 was found to be most enantioselective in the case of 4-metlioxybenzaldehyde to give (R)-alcohol in 87K yield with 80% ee. Catalysts (S)-19 and its N-methyl derivative (S)-26 gave alcohols with an (S)-absolute configuration while the N-benzylated derivative (S)-27 gave the opposite enantiomeric products. The tentative transition state models to account for the observed product stereoselectivity with morpholine ligands holding the geminal diphenyl group on the beta-amino alcohol segment are proposed. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.12.027
• 作为产物：
  描述：

  (S)-N-tert-butoxycarbonyl-4-(hydroxydiphenylmethyl)-2,2-dimethyloxazolidine 在 sodium hydroxide 、 四丁基碘化铵 、 溶剂黄146 作用下， 以 甲苯 为溶剂， 反应 27.0h， 生成 (S)-tert-butyl 2-(2-(tert-butoxycarbonylamino)-3-hydroxy-3,3-diphenylpropoxy)acetate
  参考文献：
  名称：

  Synthesis of chiral C/N-functionalized morpholine alcohols: study of their catalytic ability as ligand in asymmetric diethylzinc addition to aldehyde

  摘要：

  A broad variety of chiral C/N-functionalized morpholine alcohols sharing a common structural motif in the 3-(hydroxy-methyl)morpholine 6 were prepared froin criantiomerically pure serine for the purpose of studying their catalytic ligand properties. The asymmetric addition of diethylzinc to benzaldehyde in the presence of 10 mol % of chiral C/N-functionalized morpholine alcohols gave 1-phenyl-1-propanol in 59-81% yield with 10-30% ee. The addition of 10 mol % of n-butyl lithium to the reaction mixture resulted in a significant enhancement of the stereoselectivity in the case of ligands bearing the two geminal phenyl substituents on the backbone. In the presence of n-butyl lithium and using (S)-3-(hydroxydiphcnylmethyl)morpholine (S)-19 as the chiral promoter, (S)-1-phenyl-1 -propanol was obtained in 81% yield with 76% ee. The geminal diphenyl-class of morpholine ligands was examined for the diethylzinc addition to four different aldehydes in the presence of n-butyl lithium. (S)-N-Benzyl-3-(hydroxydiphenymethyl)morpholine (S)-27 was found to be most enantioselective in the case of 4-metlioxybenzaldehyde to give (R)-alcohol in 87K yield with 80% ee. Catalysts (S)-19 and its N-methyl derivative (S)-26 gave alcohols with an (S)-absolute configuration while the N-benzylated derivative (S)-27 gave the opposite enantiomeric products. The tentative transition state models to account for the observed product stereoselectivity with morpholine ligands holding the geminal diphenyl group on the beta-amino alcohol segment are proposed. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.12.027