(1R,3S,4R,5S)-(+)-4-benzyl-1,8,8-trimethyl-3-thiabicyclo<3.2.1>octane-3-oxide | 135608-54-7

• 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: (1R,3S,4R,5S)-(+)-4-benzyl-1,8,8-trimethyl-3-thiabicyclo<3.2.1>octane-3-oxide
• 英文别名: (1R,2S,3R,5S)-2-benzyl-1,8,8-trimethyl-3λ4-thiabicyclo[3.2.1]octane 3-oxide
• CAS: 135608-54-7
• 化学式: C₁₇H₂₄OS
• 分子量: 276.443
• InChiKey: WCSMWKAFRDVVMM-WXSAJPJJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  19.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (1R,3S,4R,5S)-(+)-4-benzyl-1,8,8-trimethyl-3-thiabicyclo<3.2.1>octane-3-oxide 在 乙酰氯 、 tin(ll) chloride 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 生成 (1R,2S,5S)-2-Benzyl-1,8,8-trimethyl-3-thia-bicyclo[3.2.1]octane
  参考文献：
  名称：

  Preparation of optically active epoxides via sulfur ylides. Origin of the chiral induction.

  摘要：

  The sulfonium ylide derived from (1R, 2S, 3R, 5S)-2,3-dibenzyl-1,8,8-trimethyl-3-thianiumbicyclo-[3.2.1]octan perchlorate 6 (prepared from (1R,3S)-(+)-camphoric acid) transfers its benzylidene group to some carbonyl compounds with ee's approaching enatiomeric purity. It is suggested that in this system the chiral induction is due to the facial selectivity at the ylide rather than the carbonyl carbon.

  DOI：

  10.1016/s0957-4166(00)82121-7
• 作为产物：
  描述：

  (1R,5S)-1,8,8-Trimethyl-3-thia-bicyclo[3.2.1]octane 在 magnesium bis(monoperoxyphthalate)hexahydrate 、 甲基锂 作用下， 以 乙醇 、 水 为溶剂， 反应 9.25h， 生成 (1R,3S,4R,5S)-(+)-4-benzyl-1,8,8-trimethyl-3-thiabicyclo<3.2.1>octane-3-oxide
  参考文献：
  名称：

  Unusual stereochemical results in the reaction of alpha-lithio derivatives of bicyclic sulfoxides

  摘要：

  The stereochemistry of the reaction of the lithio derivatives of two sets of isomeric 3-thia[3.2.1]octane-3-oxides with electrophiles such as benzyl bromide, acetone and D2O has been studied. Introduction of deuterium always occurred cis to the S=O bond as expected on the basis of earlier results described by Marquet for the related thiane-S-oxides. In contrast, benzyl groups were introduced either cis or trans to the existing S=O bond. The results are most readily rationalized in terms of a planar configuration at the a-carbanion center. The unexpected cis benzylations are due to steric hindrance of the preferred approach anti to the S=O bond by either the ethano bridge or the 8-endo methyl group.

  DOI：

  10.1016/s0040-4020(01)90458-2

文献信息

• Generation of a configurationally stable, enantioenriched α-oxy-α-methylbenzyllithium: Stereodivergence of its electrophilic substitution
  作者：Axel Carstens、Dieter Hoppe

  DOI：10.1016/s0040-4020(01)90461-2

  日期：1994.1

  of (R)- or (S)-1-phenylethyl N,N-diisopropylcarbamate with s-butyllithium/TMEDA in unpolar solvents (e.g. ether or hexane) at −78°C produces configurationally stable ion pairs which are substituted stereospecifically by different electrophiles. In several examples, complete stereoretention or inversion, respectively, was achieved. Electrophiles, which have an energetically low LUMO, such as acid chlorides

  N，N-二异丙基氨基甲酸酯的（R）-或（S）-1-苯基乙基在s-丁基锂/ TMEDA中在-78°C下进行去质子化反应生成结构稳定的离子对，这些离子对被立体定向​​取代不同的亲电试剂。在几个例子中，分别实现了完整的立体保持或反转。LUMO能量很低的亲电子试剂，例如酰氯，杂枯烯和三烷基锡氯化物，更喜欢使用前表面攻击。如果离去基团具有与锂阳离子相互作用的高趋势，例如在酯中，则发生保留的表面取代。