(+/-)-trans-2-methylene-5-t-butylcyclohexanol | 60041-30-7

• 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: (+/-)-trans-2-methylene-5-t-butylcyclohexanol
• 英文别名: (1S,5R)-5-tert-butyl-2-methylidenecyclohexan-1-ol
• CAS: 60041-30-7
• 化学式: C₁₁H₂₀O
• 分子量: 168.279
• InChiKey: MKWJZCGGUSWUQL-ZJUUUORDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  (+/-)-trans-2-methylene-5-t-butylcyclohexanol 在 二甲基硫 、 四丁基碘化铵 、 sodium hydride 、 臭氧 作用下， 以 四氢呋喃 为溶剂， 生成 (2S,4R)-2-Benzyloxy-4-tert-butyl-cyclohexanone
  参考文献：
  名称：

  Evaluation of Chelation Effects Operative during Diastereoselective Addition of the Allylindium Reagent to 2- and 3-Hydroxycyclohexanones in Aqueous, Organic, and Mixed Solvent Systems

  摘要：

  The unprotected 2- and 3-hydroxycyclohexanones 1-8 were prepared by methods that skirted as much as possible their proclivity for alpha-ketol rearrangement (where the possibility for such isomerization exists). The diastereofacial selectivity of their reaction with the allylindium reagent in water, 50% aqueous THF, and anhydrous THF is described. The neighboring alpha-hydroxyl substituent is construed to be capable of engaging in chelation, thereby controlling the stereochemical outcome of the coupling process. When the hydroxyl substituent is oriented in the equatorial plane, kinetic acceleration accompanies exclusive entry of the allyl group from the equatorial direction. Steric congestion in the vicinity of the binding hydroxyl and ketonic centers is well tolerated. Alternative projection of the OH group into the more crowded axial region may not curtail chelation. For coordination to occur, however, a twist-boat conformation must initially be adopted. While the evidence suggests that this may indeed occur in water, the necessity of crossing the added energy barrier precludes the attainment of rates that are competitive with those exhibited by the equatorial epimers (competition experiments). Placement of the hydroxyl group at C-3 provides no evident opportunity for chelation control. However, excellent stereoselectivity is seen upon axial orientation of the 3-OH group. This phenomenon is attributed to steric and/or electronic effects alone or in combination.

  DOI：

  10.1021/jo980974y
• 作为产物：
  描述：

  4-叔丁基环己酮 在 正丁基锂 、 盐酸二甲胺 、 potassium hydride 、 三甲氧基磷 作用下， 反应 4.0h， 生成 (+/-)-trans-2-methylene-5-t-butylcyclohexanol
  参考文献：
  名称：

  Hoffmann, Reinhard W.; Goldmann, Siegfried; Maak, Norbert, Chemische Berichte, 1980, vol. 113, # 3, p. 819 - 830

  摘要：

  DOI：

文献信息

• Torsional, Rotor, and Electronic Effects in 4-<i>tert</i>-Butylmethylenecyclohexane Epoxidations and Osmylations
  作者：E. Vedejs、W. H. Dent、J. T. Kendall、P. A. Oliver

  DOI：10.1021/ja953040p

  日期：1996.1.1

  The axial epoxidation preference for 2-substituted 4-tert-butylmethylenecyclohexanes is attributed to a combination of small effects, including existing bond torsion and rotor effects. Contributions from developing bond torsion are smaller and may be negligible. Cieplak (σ−σ*) effects are too small to identify in most of the epoxidations, but a marginal effect could be present according to comparisons

  2-取代 4-叔丁基亚甲基环己烷的轴向环氧化偏好归因于小效应的组合，包括现有的键扭转和转子效应。来自发展债券扭转的贡献较小，可以忽略不计。Cieplak (σ−σ*) 效应太小而无法在大多数环氧化中识别，但根据等排系统 11a 和 15a 或 19a 和 19b 的比较，可能存在边际效应。二甲基二环氧乙烷环氧化和渗透对空间因子更敏感，导致赤道攻击的趋势。
• Diastereoselective and enantioselective lipase-catalyzed hydrolysis of stereoisomeric 2-methylene, 5-t-butylcyclohexyl acetates
  作者：Chahra Bidjou、Louisa Aribi-Zouioueche、Jean-Claude Fiaud

  DOI：10.1016/s0040-4039(02)00425-2

  日期：2002.4

  cis- and trans-2-Methylene-5-t-butylcyclohexanols are obtained in high (>90%) e.e. through Rabbit Gastric Lipase (RGL)-catalyzed acylation or hydrolysis of the stereoisomeric racemic alcohols or their corresponding acetates. Since these reactions were diastereomer-selective, enantiomerically enriched cis- and trans-5-t-butyl-2-methylenecyclohexanols could also be prepared from cis/trans isomeric mixtures

  通过兔子胃脂肪酶（RGL）催化的立体异构外消旋醇或其相应乙酸酯的酰化或水解反应，可以得到高（> 90％）ee的顺式和反式-2-亚甲基-5-叔丁基环己醇。由于这些反应是非对映异构体选择性的，因此对映体富集的顺式和反式-5-叔丁基-2-亚甲基环己醇也可以由顺式/反式异构体混合物制备。
• Cambie, Richard C.; Hume, Bruce A.; Rutledge, Peter S., Journal of the Chemical Society. Perkin transactions I, 1982, p. 413 - 419
  作者：Cambie, Richard C.、Hume, Bruce A.、Rutledge, Peter S.、Woodgate, Paul D.

  DOI：——

  日期：——
• Regioselective hydroxylation of .pi.-allylpalladium complexes with the MoO2(acac)2-tert-BuOOH catalyst system
  作者：Koichiro Jitsukawa、Kiyotomi Kaneda、Shiichiro Teranishi

  DOI：10.1021/jo00151a025

  日期：1983.2
• Hoffmann, Reinhard W.; Gerlach, Rainer; Goldmann, Siegfried, Chemische Berichte, 1980, vol. 113, # 3, p. 856 - 863
  作者：Hoffmann, Reinhard W.、Gerlach, Rainer、Goldmann, Siegfried

  DOI：——

  日期：——