(1S,2S,5R)-1-(chloroacetoyl)-2-(1-methylethyl)-5-methylcyclohexan-1-ol

• 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: (1S,2S,5R)-1-(chloroacetoyl)-2-(1-methylethyl)-5-methylcyclohexan-1-ol
• 英文别名: [(1S,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] 2-chloroacetate
• 化学式: C₁₂H₂₁ClO₂
• 分子量: 232.751
• InChiKey: XHQPKRVACXDVNV-VWYCJHECSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,2S,5R)-1-(chloroacetoyl)-2-(1-methylethyl)-5-methylcyclohexan-1-ol 在 copper(II) bis(trifluoromethanesulfonate) 、 sulfur 、 三乙胺 、 2,2′-亚甲基双[(4R,5S)-4,5-二苯基-2-噁唑啉] 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 17.5h， 生成 (1S,2S,5R)-2-isopropyl-5-methyl-cyclohexyl 4,5-dimethyl-2-(methylsulfanyl)-3,6-dihydro-2H-thiopyran-2-carboxylate
  参考文献：
  名称：

  Asymmetric diastereoselective thia-hetero-Diels–Alder reactions of dithioesters

  摘要：

  Asymmetric thia-Diels-Alder reactions involving new dithioesters bearing a chiral auxiliary are described, with diastereoselectivities up to 78%. Double-stereodifferentiating experiments employing chiral substrates in the presence of a chiral Lewis acid catalyst have been also carried out and, in this case, a diastereomeric excess of 90% was reached. The absolute stereochemistry of cycloadducts resulting from dithiooxalates and carbonyloxazolidinone dithioesters was assigned based on an X-ray structure and chemical correlation. In order to rationalize the sense of the chiral induction, stereochemical models for Cu(II)/bis(oxazoline)/dithioester complexes are proposed. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.01.039
• 作为产物：
  描述：

  L-薄荷醇 、 氯乙酸 在 偶氮二甲酸二异丙酯 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 以62%的产率得到(1S,2S,5R)-1-(chloroacetoyl)-2-(1-methylethyl)-5-methylcyclohexan-1-ol
  参考文献：
  名称：

  吡啶甲酸作为Mitsunobu反应的伴侣：随后在甲醇溶液中，基本上在中性条件下用乙酸铜水解吡啶甲酸酯

  摘要：

  已经研究了在Mitsunobu反应中使用吡啶甲酸和6-甲基吡啶甲酸。这些底物是Mitsunobu反应的极好伙伴，并提供了额外的优势，即所产生的酯可以在基本中性的条件下使用Cu（OAc）2和甲醇裂解。

  DOI：

  10.1016/s0040-4039(99)00332-9

文献信息

• Effect of the acidic component on the Mitsunobu inversion of a sterically hindered alcohol
  作者：Jeffrey A. Dodge、John I. Trujillo、Misti Presnell

  DOI：10.1021/jo00080a039

  日期：1994.1
• Asymmetric diastereoselective thia-hetero-Diels–Alder reactions of dithioesters
  作者：Hélène Dentel、Isabelle Chataigner、Jean-François Lohier、Mihaela Gulea

  DOI：10.1016/j.tet.2012.01.039

  日期：2012.3

  Asymmetric thia-Diels-Alder reactions involving new dithioesters bearing a chiral auxiliary are described, with diastereoselectivities up to 78%. Double-stereodifferentiating experiments employing chiral substrates in the presence of a chiral Lewis acid catalyst have been also carried out and, in this case, a diastereomeric excess of 90% was reached. The absolute stereochemistry of cycloadducts resulting from dithiooxalates and carbonyloxazolidinone dithioesters was assigned based on an X-ray structure and chemical correlation. In order to rationalize the sense of the chiral induction, stereochemical models for Cu(II)/bis(oxazoline)/dithioester complexes are proposed. (C) 2012 Elsevier Ltd. All rights reserved.
• Picolinic acid as a partner in the Mitsunobu reaction: Subsequent hydrolysis of picolinate esters under essentially neutral conditions with copper acetate in methanol
  作者：Tarek Sammakia、Jon S. Jacobs

  DOI：10.1016/s0040-4039(99)00332-9

  日期：1999.4

  The use of picolinic acid and 6-methyl picolinic acid in the Mitsunobu reaction has been studied. These substrates are excellent partners in the Mitsunobu reaction, and offer the added advantage that the resulting esters can be cleaved under essentially neutral conditions using Cu(OAc)2 and methanol.

  已经研究了在Mitsunobu反应中使用吡啶甲酸和6-甲基吡啶甲酸。这些底物是Mitsunobu反应的极好伙伴，并提供了额外的优势，即所产生的酯可以在基本中性的条件下使用Cu（OAc）2和甲醇裂解。