benzyl nopyl sulfide | 132410-30-1

• 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: benzyl nopyl sulfide
• CAS: 132410-30-1
• 化学式: C₁₈H₂₄S
• 分子量: 272.455
• InChiKey: NPZVOTTYJYOHMZ-IRXDYDNUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  19.0
• 可旋转键数：
  5.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  (1R)6,6-二甲基联环(3.1.1)庚烷-2-烯-2-乙醇 在 吡啶 、 氢氧化钾 作用下， 反应 44.5h， 生成 benzyl nopyl sulfide
  参考文献：
  名称：

  Asymmetric reductions of prochiral ketones with lithium [2-[2-benzyloxy)ethyl]-6,6-dimethylbicyclo[3.1.1]-3-nonyl]-9-boratabicyclo-[3.3.1]nonane (lithium NB-Enantride) and its derivatives

  摘要：

  NB-Enantride, prepared by hydroboration of nopyl benzyl ether with 9-borabicyclo[3.3.1]nonane (9-BBN) followed by treatment with tert-butyllithium, is an effective asymmetric reducing agent. Especially noteworthy is the fact that it can reduce aliphatic ketones such as 2-octanone or 2-butanone in efficiencies approaching 80% enantiomeric excess. Several analogues have been tested in order to probe the structural features which contribute to making this reagent effective. The ether group evidently plays a role in obtaining high selectivity, since changing oxygen to nitrogen or sulfur causes a drop in selectivity. Moving the ether group by one atom in either direction or making it more hindered causes a drop in selectivity. However, replacing the OCH2C6H5 group with a methyl group also results in an effective reducing agent and suggests that steric factors play an important role. The lithium cation was also found to be very important. Whereas the lithium compound reduced acetophenone within minutes at -78-degrees-C, the potassium analogue gave no reduction over an extended period. At higher temperatures (-65-degrees-C) reduction did slowly occur with the potassium compound, but the selectivity was greatly reduced in comparison to the lithium compound.

  DOI：

  10.1021/jo00003a030

文献信息

• First study of rhodium(I) complexes with chiral sulfur-containing terpenoids as catalytic systems for ketone hydrosilylation
  作者：Vladimir M. Uvarov、Dimitry A. de Vekki

  DOI：10.1080/10426507.2019.1700376

  日期：2020.5.3

  a number of chiral thiolate and sulfide ligands based on natural terpenes and terpenoids have been synthesized in a few simple steps. Two new Rh-thiolate complexes with the formula [Rh(CO)2(μ-SR)]2 were obtained. The influence of these complexes and catalytic systems formed by combining the synthesized ligands with [Rh(CO)2(μ-Cl)]2 and [Rh(cod)(μ-Cl)]2, on the reaction rate, chemoselectivity, stereoselectivity

  摘要 使用“手性池”方法，通过几个简单的步骤合成了许多基于天然萜烯和萜类化合物的手性硫醇盐和硫化物配体。获得了两种新的具有式[Rh(CO)2(μ-SR)]2的Rh-硫醇盐配合物。合成配体与[Rh(CO)2(μ-Cl)]2和[Rh(cod)(μ-Cl)]2结合形成的配合物和催化体系对反应速率、化学选择性、立体选择性的影响已经研究了在 Rh 催化的苯乙酮不对称氢化硅烷化中四苯基二硅氧烷的形成作为模型反应。介绍了在含 S 配体存在下形成作为副产物的甲硅烷基烯醇醚的机理方面。图形概要