trans-4,4-dimethyl-2-(1-propenyl)-1,3-oxathiane | 561329-05-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧硫烷类
• 英文名称: trans-4,4-dimethyl-2-(1-propenyl)-1,3-oxathiane
• 英文别名: 4,4-dimethyl-2-[(E)-prop-1-enyl]-1,3-oxathiane
• CAS: 561329-05-3
• 化学式: C₉H₁₆OS
• 分子量: 172.291
• InChiKey: GMWBXUNHZVMEBY-SNAWJCMRSA-N

物化性质

• 沸点：
  226.2±40.0 °C(Predicted)
• 密度：
  1.005±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  34.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,1-二苯乙烯 、 trans-4,4-dimethyl-2-(1-propenyl)-1,3-oxathiane 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以37%的产率得到4-methyl-2,2-diphenyl-3,4-dihydro-2H-thiopyran
  参考文献：
  名称：

  A novel tandem [4++2] cycloaddition–elimination reaction: 2-alkenyl-4,4-dimethyl-1,3-oxathianes as synthetic equivalents for α,β-unsaturated thioaldehydes

  摘要：

  The first tandem cationic [4(+)+2] polar cycloaddition-elimination reaction of 1-thia-1,3-butadienyl cations B with olefins to afford directly 3,4-dihydro-2H-thiopyrans D is described. The cations B were easily accessible by treatment of monothioacetals A, particularly the 2-alkenyl-4,4-dimethyl-1,3-oxathianes 1, with a hard Lewis acid. In this novel reaction, 2-alkenyl-4,4-dimethyl-1,3-oxathianes were utilized as synthetic equivalents for highly reactive alpha,beta-unsaturated thioaldehydes. The effect of geminal dimethyl substituents on the oxathianes 1 and the mechanistic aspect of the reaction are considered. The reaction's asymmetric version was also investigated using a chiral oxathiane 4 derived from (-)-(IR,2R,5R)-2-(I-mercapto-l-methylethyl)-5-methylcyclohexanol. Although the enantioselectivities were moderate, the whole process can be done under odorless conditions. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00179-0
• 作为产物：
  描述：

  3-甲基-2-丁烯酸乙酯 在 lithium aluminium tetrahydride 、 sodium ethanolate 、 lithium perchlorate 、 sodium 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 氨 为溶剂， 反应 111.0h， 生成 trans-4,4-dimethyl-2-(1-propenyl)-1,3-oxathiane
  参考文献：
  名称：

  A novel tandem [4++2] cycloaddition–elimination reaction: 2-alkenyl-4,4-dimethyl-1,3-oxathianes as synthetic equivalents for α,β-unsaturated thioaldehydes

  摘要：

  The first tandem cationic [4(+)+2] polar cycloaddition-elimination reaction of 1-thia-1,3-butadienyl cations B with olefins to afford directly 3,4-dihydro-2H-thiopyrans D is described. The cations B were easily accessible by treatment of monothioacetals A, particularly the 2-alkenyl-4,4-dimethyl-1,3-oxathianes 1, with a hard Lewis acid. In this novel reaction, 2-alkenyl-4,4-dimethyl-1,3-oxathianes were utilized as synthetic equivalents for highly reactive alpha,beta-unsaturated thioaldehydes. The effect of geminal dimethyl substituents on the oxathianes 1 and the mechanistic aspect of the reaction are considered. The reaction's asymmetric version was also investigated using a chiral oxathiane 4 derived from (-)-(IR,2R,5R)-2-(I-mercapto-l-methylethyl)-5-methylcyclohexanol. Although the enantioselectivities were moderate, the whole process can be done under odorless conditions. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00179-0

文献信息

• A novel tandem [4++2] cycloaddition–elimination reaction: 2-alkenyl-4,4-dimethyl-1,3-oxathianes as synthetic equivalents for α,β-unsaturated thioaldehydes
  作者：Shin-ichi Ohsugi、Kiyoharu Nishide、Manabu Node

  DOI：10.1016/s0040-4020(03)00179-0

  日期：2003.3

  The first tandem cationic [4(+)+2] polar cycloaddition-elimination reaction of 1-thia-1,3-butadienyl cations B with olefins to afford directly 3,4-dihydro-2H-thiopyrans D is described. The cations B were easily accessible by treatment of monothioacetals A, particularly the 2-alkenyl-4,4-dimethyl-1,3-oxathianes 1, with a hard Lewis acid. In this novel reaction, 2-alkenyl-4,4-dimethyl-1,3-oxathianes were utilized as synthetic equivalents for highly reactive alpha,beta-unsaturated thioaldehydes. The effect of geminal dimethyl substituents on the oxathianes 1 and the mechanistic aspect of the reaction are considered. The reaction's asymmetric version was also investigated using a chiral oxathiane 4 derived from (-)-(IR,2R,5R)-2-(I-mercapto-l-methylethyl)-5-methylcyclohexanol. Although the enantioselectivities were moderate, the whole process can be done under odorless conditions. (C) 2003 Elsevier Science Ltd. All rights reserved.