2-hydroxymethyl-3-cyclohexyliden-propan-1-ol | 77192-46-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-hydroxymethyl-3-cyclohexyliden-propan-1-ol
• 英文别名: 2-(cyclohexylidene)propane-1,3-diol；1,3-Propanediol, 2-(cyclohexylidenemethyl)-；2-(cyclohexylidenemethyl)propane-1,3-diol
• CAS: 77192-46-2
• 化学式: C₁₀H₁₈O₂
• 分子量: 170.252
• InChiKey: RXZDGSTUBHYHQL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-hydroxymethyl-3-cyclohexyliden-propan-1-ol 在 palladium on activated charcoal N-[(2,4-二氯苯氧基)-甲氧基硫代膦酰]丙-2-胺 、 氢气 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 生成 2-(环己基甲基)丙烷-1,3-二基二乙酸酯
  参考文献：
  名称：

  Chemoenzymic preparation of asymmetrized tris(hydroxymethyl)methane (THYM*) and of asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*) as new highly versatile chiral building blocks

  摘要：

  A series of asymmetrized tris(hydroxymethyl)methanes 2 and bis(hydroxymethyl)acetaldehydes 3 have been prepared in both enantiomeric forms through a chemoenzymatic methodology. The key step is the highly enantioselective PPL-catalyzed monohydrolysis of 2(E)-alkenyl-1,3-diacetoxypropanes 25-27. A careful study on the effect of unsaturations adjacent to the prochiral center in a series of 2-substituted 1,3-diacetoxypropanes has confirmed the suggested beneficial effect of a pi-system in that position but has also unveiled an unprecedented dramatic effect of double-bond configuration on enantioselectivity. A new empirical model for the interpretation of these and other results, based both on polarity and steric arguments, is proposed. This study provides a general protocol for the efficient synthesis of asymmetrized 1,3-propanediols bearing in position 2 saturated or unsaturated carbon chains.

  DOI：

  10.1021/jo00031a039
• 作为产物：
  描述：

  (2,3-epoxypropylidene)cyclohexane 在 lithium aluminium tetrahydride 、 五羰基铁 、 ammonium cerium(IV) nitrate 作用下， 以 乙醚 为溶剂， 生成 2-hydroxymethyl-3-cyclohexyliden-propan-1-ol
  参考文献：
  名称：

  通过三羰基铁-内酯配合物制备内酯

  摘要：

  通过五羰基铁的处理，已经从乙烯基环氧乙烷中制备了许多三羰基铁-内酯配合物。在某些情况下，两个η 3 -烯丙基配合物进行了从单一乙烯基环氧乙烷分离。硝酸铈（IV）铵在乙腈中对络合物的氧化主要导致β-内酯。初始配合物的立体化学完整性反映在氧化产物的形成中。用氢化铝锂还原这些产物得到预期的二醇。

  DOI：

  10.1039/p19810000270

文献信息

• A Short Access to 3-Hydroxy-4-hydroxymethyltetrahydrofurans: Application to the Total Synthesis of Amphiasterin B4
  作者：Hani Salim、Olivier Piva

  DOI：10.1021/jo8020659

  日期：2009.3.6

  The first total synthesis of amphiasterin B4, a secondary metabolite previously isolated from Plakortisquasiamphiaster has been achieved. The core structure has been reached according to a highly stereoselective one-pot epoxidation/cyclization of an unsaturated diol. This substrate can be prepared from β,γ-unsaturated diesters readily available from the organocatalyzed protonation of a transient dienol

  已经完成了两性代谢物amphiasterin B4的首次合成，后者是先前从Plakortis quasiamphiaster中分离出来的次级代谢产物。根据不饱和二醇的高度立体选择性的一锅环氧化/环化，已经达到了核心结构。该底物可以由β，γ-不饱和二酯制备，所述β，γ-不饱和二酯可容易地得自通过相应的α，β-不饱和异构体的UV辐射而产生的过渡二烯醇的有机催化质子化。
• Enzymes in organic synthesis: remarkable influence of a π system on the enantioselectivity in PPL catalysed monohydrolysis of 2-substituted 1,3-diacetoxypropanes.
  作者：Giuseppe Guanti、Luca Banfi、Enrica Narisano

  DOI：10.1016/s0957-4166(00)82383-6

  日期：1990.1
• Preparation of lactones via tricarbonyliron–lactone complexes
  作者：Gary D. Annis、Steven V. Ley、Christopher R. Self、Ramamoorthy Sivaramakrishnan

  DOI：10.1039/p19810000270

  日期：——

  A number of tricarbonyliron–lactone complexes have been prepared from vinyl oxirans by treatment with pentacarbonyliron. In certain cases two η3-allyl complexes were isolated from a single vinyl oxiran. Oxidation of the complexes by cerium(IV) ammonium nitrate in acetonitrile leads predominantly to β-lactones. The stereochemical integrity of the initial complexes is reflected in the formation of the

  通过五羰基铁的处理，已经从乙烯基环氧乙烷中制备了许多三羰基铁-内酯配合物。在某些情况下，两个η 3 -烯丙基配合物进行了从单一乙烯基环氧乙烷分离。硝酸铈（IV）铵在乙腈中对络合物的氧化主要导致β-内酯。初始配合物的立体化学完整性反映在氧化产物的形成中。用氢化铝锂还原这些产物得到预期的二醇。
• Chemoenzymic preparation of asymmetrized tris(hydroxymethyl)methane (THYM*) and of asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*) as new highly versatile chiral building blocks
  作者：Giuseppe Guanti、Luca Banfi、Enrica Narisano

  DOI：10.1021/jo00031a039

  日期：1992.2

  A series of asymmetrized tris(hydroxymethyl)methanes 2 and bis(hydroxymethyl)acetaldehydes 3 have been prepared in both enantiomeric forms through a chemoenzymatic methodology. The key step is the highly enantioselective PPL-catalyzed monohydrolysis of 2(E)-alkenyl-1,3-diacetoxypropanes 25-27. A careful study on the effect of unsaturations adjacent to the prochiral center in a series of 2-substituted 1,3-diacetoxypropanes has confirmed the suggested beneficial effect of a pi-system in that position but has also unveiled an unprecedented dramatic effect of double-bond configuration on enantioselectivity. A new empirical model for the interpretation of these and other results, based both on polarity and steric arguments, is proposed. This study provides a general protocol for the efficient synthesis of asymmetrized 1,3-propanediols bearing in position 2 saturated or unsaturated carbon chains.