d-menthyl 2-chloro-1,2,3,4-tetrahydro-1-hydroxynaphthalene-2-carboxylate | 1381801-02-0

• 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-chloro-1,2,3,4-tetrahydro-1-hydroxynaphthalene-2-carboxylate
• CAS: 1381801-02-0
• 化学式: C₂₁H₂₉ClO₃
• 分子量: 364.912
• InChiKey: YKGBQZWIUJLPGK-DJNKVENRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.65
• 重原子数：
  25.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  d-menthyl 2-chloro-1,2,3,4-tetrahydro-1-hydroxynaphthalene-2-carboxylate 、 3,5-双三氟甲基苯甲酰氯 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以91%的产率得到d-menthyl 1-[3,5-bis(trifluoromethyl)benzoyloxy]-2-chloro-1,2,3,4-tetrahydronaphthalene-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 、 C₃₄H₂₄N₂O 、 copper(II) bis(trifluoromethanesulfonate) 、 lithium tri-t-butoxyaluminum hydride 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 2.0h， 生成 d-menthyl 2-chloro-1,2,3,4-tetrahydro-1-hydroxynaphthalene-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