d-menthyl 2-azido-1,2,3,4-tetrahydro-1-oxonaphthalene-2-carboxylate | 1381801-01-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: d-menthyl 2-azido-1,2,3,4-tetrahydro-1-oxonaphthalene-2-carboxylate
• CAS: 1381801-01-9
• 化学式: C₂₁H₂₇N₃O₃
• 分子量: 369.464
• InChiKey: MTIMQLFLMCXRRZ-DJXDEVDJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.87
• 重原子数：
  27.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  92.13
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  d-menthyl 2-azido-1,2,3,4-tetrahydro-1-oxonaphthalene-2-carboxylate 在 二异丁基氢化铝 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以41%的产率得到d-menthyl 2-azido-1,2,3,4-tetrahydro-1-hyroxynaphthalene-2-carboxylate
  参考文献：
  名称：

  Highly Enantioselective Chlorination of β-Keto Esters and Subsequent S_N2 Displacement of Tertiary Chlorides: A Flexible Method for the Construction of Quaternary Stereogenic Centers

  摘要：

  Highly enantioselective chlorination of beta-oxo esters and subsequent stereospecific substitution of tertiary chlorides are described. Enantioselective chlorination of beta-keto esters and malonates was performed using a chiral Lewis acid catalyst prepared from Cu(OTf)(2) and the newly developed spirooxazoline ligand 2 to yield the desired a-chlorinated products with high enantioselectivity (up to 98% ee). Nucleophilic substitution of the resulting chlorides proceeded smoothly to afford a variety of chiral molecules such as alpha-amino, alpha-allcylthio, and alpha-fluoro esters, without loss of enantiopurity. The results of X-ray crystallographic analysis proved that Walden inversion occurs at the chlorinated tertiary carbon center. These results supported the fact that the substitution proceeds via an S(N)2 mechanism.

  DOI：

  10.1021/ja304806j
• 作为产物：
  描述：

  D-薄荷醇 在 4-二甲氨基吡啶 、 N-氯代丁二酰亚胺 、 sodium azide 、 C₃₄H₂₄N₂O 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 二甲基亚砜 、 苯 为溶剂， 反应 4.0h， 生成 d-menthyl 2-azido-1,2,3,4-tetrahydro-1-oxonaphthalene-2-carboxylate
  参考文献：
  名称：

  Highly Enantioselective Chlorination of β-Keto Esters and Subsequent S_N2 Displacement of Tertiary Chlorides: A Flexible Method for the Construction of Quaternary Stereogenic Centers

  摘要：

  Highly enantioselective chlorination of beta-oxo esters and subsequent stereospecific substitution of tertiary chlorides are described. Enantioselective chlorination of beta-keto esters and malonates was performed using a chiral Lewis acid catalyst prepared from Cu(OTf)(2) and the newly developed spirooxazoline ligand 2 to yield the desired a-chlorinated products with high enantioselectivity (up to 98% ee). Nucleophilic substitution of the resulting chlorides proceeded smoothly to afford a variety of chiral molecules such as alpha-amino, alpha-allcylthio, and alpha-fluoro esters, without loss of enantiopurity. The results of X-ray crystallographic analysis proved that Walden inversion occurs at the chlorinated tertiary carbon center. These results supported the fact that the substitution proceeds via an S(N)2 mechanism.

  DOI：

  10.1021/ja304806j