(+/-)-1-methyl-4r-isopropyl-cyclohexen-(1)-ol-(5c)

• 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: (+/-)-1-methyl-4r-isopropyl-cyclohexen-(1)-ol-(5c)
• 英文别名: (1R,6R)-3-methyl-6-propan-2-ylcyclohex-3-en-1-ol
• 化学式: C₁₀H₁₈O
• 分子量: 154.252
• InChiKey: UDQXLNRIDGDFAR-NXEZZACHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-1-methyl-4r-isopropyl-cyclohexen-(1)-ol-(5c) 生成 (+/-)-5c-(4-nitro-benzoyloxy)-1-methyl-4r-isopropyl-cyclohexene-(1)
  参考文献：
  名称：

  41.关于薄荷酮系列的研究。第十四部分。DL -1-Hydroxymenthone，DL -薄荷-1：3-二醇，以及DL -A- 6 -新薄荷烯-3-醇

  摘要：

  DOI：

  10.1039/jr9370000237
• 作为产物：
  描述：

  (R)-(+)-2-isopropyl-5-methylhex-5-en-1-ol 在 草酰氯 、 titanocene(IV) triflate 、 二甲基亚砜 、 三乙胺 作用下， 以 硝基甲烷 、 二氯甲烷 为溶剂， 反应 0.67h， 生成 (+/-)-1-methyl-4r-isopropyl-cyclohexen-(1)-ol-(5c)
  参考文献：
  名称：

  Asymmetric synthesis and Lewis acid mediated type II carbonyl ene cyclisations of (R)-2-isopropyl-5-methylhex-5-enal

  摘要：

  The asymmetric synthesis of (R)-2-isopropyl-5-methylhex-5-enal in 98% ee is described. It was discovered that the key alkylation step employing an Evans chiral auxiliary and 3-methylbut-3-en-1-yl trifluoromethanesulphonate as the alkylating agent led to significant competing O-alkylation, a phenomenon not previously reported. Type II carbonyl ene cyclisation of the aldehyde with a range of Lewis acids led to either the (R,R)- or (R,S)-5-methylidenecyclohexanols without concurrent racemisation of the alpha stereogenic centre of the aldehyde. Conditions for effecting the easy racemisation of a model enantiomerically pure aldehyde, (S)-2-methylbutanal, were developed. In an effort to secure a dynamic kinetic resolution procedure, these conditions were applied to (R)-2-isopropyl-5-methylhex-5-enal. However, a competing and dominant Prins cyclisation occurred instead leading to a mixture of all possible cycloadducts, all of which were obtained in 98% ee. Any unreacted aldehyde was found to be enantiomerically pure. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00316-5

文献信息

• Inagaki, Takashi; Ueda, Hiroo, Agricultural and Biological Chemistry, 1987, vol. 51, # 10, p. 2635 - 2640
  作者：Inagaki, Takashi、Ueda, Hiroo

  DOI：——

  日期：——
• Models for the Carbonyl-ene Cyclization Reaction: Open and Closed Transition States
  作者：D. Christopher Braddock、King Kuok (Mimi) Hii、John M. Brown

  DOI：10.1002/(sici)1521-3773(19980703)37:12<1720::aid-anie1720>3.0.co;2-w

  日期：1998.7.3

  Different cyclization products are formed with different Lewis acids in the ene cyclization of 5-hexenals (see scheme on the right; a: methylaluminum bisphenoxide, b: Me2 AlCl, c: Sc(OSO2 CF3 )3 ). This is not surprising, but it is gratifying that these result can be rationalized with an internally consistent model.
• 41. Researches in the menthone series. Part XIV. dl-1-Hydroxymenthone, dl-menthane-1 : 3-diols, and dl-â—�⁶-neomenthen-3-ol
  作者：John Read、Geoffrey Swann

  DOI：10.1039/jr9370000237

  日期：——
• Asymmetric synthesis and Lewis acid mediated type II carbonyl ene cyclisations of (R)-2-isopropyl-5-methylhex-5-enal
  作者：D.Christopher Braddock、John M Brown

  DOI：10.1016/s0957-4166(00)00316-5

  日期：2000.9

  The asymmetric synthesis of (R)-2-isopropyl-5-methylhex-5-enal in 98% ee is described. It was discovered that the key alkylation step employing an Evans chiral auxiliary and 3-methylbut-3-en-1-yl trifluoromethanesulphonate as the alkylating agent led to significant competing O-alkylation, a phenomenon not previously reported. Type II carbonyl ene cyclisation of the aldehyde with a range of Lewis acids led to either the (R,R)- or (R,S)-5-methylidenecyclohexanols without concurrent racemisation of the alpha stereogenic centre of the aldehyde. Conditions for effecting the easy racemisation of a model enantiomerically pure aldehyde, (S)-2-methylbutanal, were developed. In an effort to secure a dynamic kinetic resolution procedure, these conditions were applied to (R)-2-isopropyl-5-methylhex-5-enal. However, a competing and dominant Prins cyclisation occurred instead leading to a mixture of all possible cycloadducts, all of which were obtained in 98% ee. Any unreacted aldehyde was found to be enantiomerically pure. (C) 2000 Elsevier Science Ltd. All rights reserved.