6-methyl-1-oxa-4-thiaspiro<4.5>dec-6-ene-7-carbaldehyde | 207108-07-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: 6-methyl-1-oxa-4-thiaspiro<4.5>dec-6-ene-7-carbaldehyde
• 英文别名: 6-Methyl-1-oxa-4-thiaspiro[4.5]dec-6-ene-7-carbaldehyde
• CAS: 207108-07-4
• 化学式: C₁₀H₁₄O₂S
• 分子量: 198.286
• InChiKey: NFJWACMMZRGBAG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-methyl-1-oxa-4-thiaspiro<4.5>dec-6-ene-7-carbaldehyde 在 lithium aluminium tetrahydride 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 9.5h， 生成 2-((5R,6R)-6-Methyl-7-methylene-1-oxa-4-thia-spiro[4.5]dec-6-yl)-ethanol
  参考文献：
  名称：

  7-羟甲基-6-甲基-1-氧杂-4-硫杂螺[4.5] dec-6-烯。在Johnson Ortho Ester Claisen重排有利于Cieplak非对映选择的条件下，具有极高的抗硫非对映选择性。

  摘要：

  DOI：

  10.1021/jo981634f
• 作为产物：
  描述：

  N,N-二甲基甲酰胺 、 7-Bromo-6-methyl-1-oxa-4-thiaspiro[4.5]dec-6-ene 在 正丁基锂 作用下， 生成 6-methyl-1-oxa-4-thiaspiro<4.5>dec-6-ene-7-carbaldehyde
  参考文献：
  名称：

  An Investigation of the Diastereoselectivity of Nucleophilic Additions to 6-Methyl-1-oxa-4-thiaspiro[4.5]dec-6-ene-7-carbaldehyde. Hybridization of the Nucleophile Alters the Diastereoselectivity

  摘要：

  6-Methyl-1-oxa-4-thiaspiro[4.5]dec-6-ene-7-carbaldehyde was treated with a variety of nucleophiles under varying conditions. Whereas the 1,4-diastereoselectivity observed with sp(3) nucleophiles was more or less 1.0:1.1 in favor of attack anti to sulfur, sp(2) and sp nucleophiles exhibited relatively much improved but reversed pi-selection under the same conditions. The highest selectivity observed was 3.5:1.0 in favor of attack syn to sulfur in reaction with PhMgBr in Et2O at -80 degrees C. This selectivity was reduced to 1.6:1.0 when the reaction was conducted in a 9:1 mixture of Et2O and HMPA but enhanced to 7.2:1.0 when the polarity of the reaction medium was reduced by conducting the reaction in a 1:1 mixture of Et2O and n-hexane. Neither the anti to S nor the syn to S diastereoselectivity obeyed the dipole model reported by Wipf and Kim. The syn to S selectivity in reactions with sp(2) and sp nucleophiles may be a result of significant and yet specific electrostatic attraction of S for these nucleophilic species which have their negative charges concentrated largely on the carbon for their known significant polar characters.

  DOI：

  10.1021/jo971697i

文献信息

• An Investigation of the Diastereoselectivity of Nucleophilic Additions to 6-Methyl-1-oxa-4-thiaspiro[4.5]dec-6-ene-7-carbaldehyde. Hybridization of the Nucleophile Alters the Diastereoselectivity
  作者：Duraiswamy A. Jeyaraj、Veejendra K. Yadav、Masood Parvez、Harsh M. Gauniyal

  DOI：10.1021/jo971697i

  日期：1998.6.1

  6-Methyl-1-oxa-4-thiaspiro[4.5]dec-6-ene-7-carbaldehyde was treated with a variety of nucleophiles under varying conditions. Whereas the 1,4-diastereoselectivity observed with sp(3) nucleophiles was more or less 1.0:1.1 in favor of attack anti to sulfur, sp(2) and sp nucleophiles exhibited relatively much improved but reversed pi-selection under the same conditions. The highest selectivity observed was 3.5:1.0 in favor of attack syn to sulfur in reaction with PhMgBr in Et2O at -80 degrees C. This selectivity was reduced to 1.6:1.0 when the reaction was conducted in a 9:1 mixture of Et2O and HMPA but enhanced to 7.2:1.0 when the polarity of the reaction medium was reduced by conducting the reaction in a 1:1 mixture of Et2O and n-hexane. Neither the anti to S nor the syn to S diastereoselectivity obeyed the dipole model reported by Wipf and Kim. The syn to S selectivity in reactions with sp(2) and sp nucleophiles may be a result of significant and yet specific electrostatic attraction of S for these nucleophilic species which have their negative charges concentrated largely on the carbon for their known significant polar characters.
• 7-Hydroxymethyl-6-methyl-1-oxa-4-thiaspiro[4.5]dec-6-ene. Exceptionally High Anti to Sulfur Diastereoselectivity under Conditions of Johnson Ortho Ester Claisen Rearrangement Favors Cieplak Mode of Diastereoselection
  作者：Veejendra K. Yadav、Duraiswamy A. Jeyaraj、Masood Parvez、Raghav Yamdagni

  DOI：10.1021/jo981634f

  日期：1999.4.1