2-<(S)-2-octyl>-1,3-dithiane | 131545-91-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二噻烷
• 英文名称: 2-<(S)-2-octyl>-1,3-dithiane
• 英文别名: 2-[(2S)-octan-2-yl]-1,3-dithiane
• CAS: 131545-91-0
• 化学式: C₁₂H₂₄S₂
• 分子量: 232.455
• InChiKey: GSBNYDZTQJFJRJ-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-<(S)-2-octyl>-1,3-dithiane 在 sodium periodate 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 生成 (1R,2S)-2-((S)-1-Methyl-heptyl)-[1,3]dithiane 1-oxide 、 (1S,2S)-2-((S)-1-Methyl-heptyl)-[1,3]dithiane 1-oxide
  参考文献：
  名称：

  Single electron transfer mechanism in the reaction of 1,3-dithianyllithium and alkyl iodides

  摘要：

  The reaction between 2-lithio-1,3-dithiane and optically active (R)-2-iodooctane was found to proceed with complete inversion of configuration. This result suggests that the S(N)2 (rather than single electron transfer (SET) mechanism is the preferred pathway for reaction between dithianyllithium and unhindered alkyl halides. When the neopentyl-type radical probe 5,5-dimethyl-6-iodo-1-hexene was used as the substrate halide, 6-11% cyclized alkylated product was obtained. This result suggests that when the S(N)2 pathway is blocked, SET mechanisms become operative to some extent, at least with iodide as the halogen. The reaction of dithianyllithium and (R)-2-iodooctane and 5,5-dimethyl-6-iodo-1-hexene, with hexane as the solvent, proceeds under heterogeneous conditions to bring about complete racemization or cyclization of the respective iodide. These results demonstrate for the first time that 2-lithio-1,3-dithiane can act as electron donor in reactions initiated by electron transfer to alkyl iodides.

  DOI：

  10.1021/jo00004a051
• 作为产物：
  描述：

  2-lithio-1,3-dithiane 、 (R)-(-)-2-iodooctane 以 四氢呋喃 为溶剂， 以45%的产率得到2-<(S)-2-octyl>-1,3-dithiane
  参考文献：
  名称：

  Single electron transfer mechanism in the reaction of 1,3-dithianyllithium and alkyl iodides

  摘要：

  The reaction between 2-lithio-1,3-dithiane and optically active (R)-2-iodooctane was found to proceed with complete inversion of configuration. This result suggests that the S(N)2 (rather than single electron transfer (SET) mechanism is the preferred pathway for reaction between dithianyllithium and unhindered alkyl halides. When the neopentyl-type radical probe 5,5-dimethyl-6-iodo-1-hexene was used as the substrate halide, 6-11% cyclized alkylated product was obtained. This result suggests that when the S(N)2 pathway is blocked, SET mechanisms become operative to some extent, at least with iodide as the halogen. The reaction of dithianyllithium and (R)-2-iodooctane and 5,5-dimethyl-6-iodo-1-hexene, with hexane as the solvent, proceeds under heterogeneous conditions to bring about complete racemization or cyclization of the respective iodide. These results demonstrate for the first time that 2-lithio-1,3-dithiane can act as electron donor in reactions initiated by electron transfer to alkyl iodides.

  DOI：

  10.1021/jo00004a051

文献信息

• A Temporary Stereocentre Approach for the Stereodivergent Synthesis of Either Enantiomer of α-Methyloctanal
  作者：D. Gangani Niyadurupola、Iwan R. Davies、Richard Wisedale、Steven D. Bull

  DOI：10.1002/ejoc.200700782

  日期：2007.11

  The aldol reaction of a chiral N-(acyl)oxazolidin-2-one with 2-methyleneoctanal or (E)-2-methyloct-2-enal affords chiral aldol products whose alkene functionalities were hydrogenated using Brown's or Wilkinson's catalyst to afford syn- or anti-selective products with excellent levels of diastereocontrol. Subsequent retro-aldol cleavage of these syn- or anti-adducts resulted in the formation of either

  手性 N-(酰基) 恶唑烷-2-one 与 2-亚甲基辛醛或 (E)-2-methyloct-2-enal 的羟醛反应提供手性羟醛产物，其烯烃官能团使用布朗或威尔金森催化剂氢化以提供合成-或具有出色非对映控制水平的抗选择性产品。随后这些顺式或反加合物的逆羟醛裂解导致形成 α-甲基辛醛的 (R)-或 (S)-对映异构体，没有发生外消旋化，可以原位衍生化以提供手性对映体纯形式的二噻烷、醇或 α,β-不饱和酯产品。
• JUARISTI, EUSEBIO;JIMENEZ-VAZQUEZ, HUGO A., J. ORG. CHEM., 56,(1991) N, C. 1623-1630
  作者：JUARISTI, EUSEBIO、JIMENEZ-VAZQUEZ, HUGO A.

  DOI：——

  日期：——