(1S,2R,5R,7S,9R)-10,10-Dimethyl-5-phenyl-4-oxa-6-thia-tricyclo[7.1.1.0^2,7]undecane | 599192-49-1

• 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: (1S,2R,5R,7S,9R)-10,10-Dimethyl-5-phenyl-4-oxa-6-thia-tricyclo[7.1.1.0^2,7]undecane
• 英文别名: (1S,2R,5R,7S,9R)-10,10-dimethyl-5-phenyl-4-oxa-6-thiatricyclo[7.1.1.02,7]undecane
• CAS: 599192-49-1
• 化学式: C₁₇H₂₂OS
• 分子量: 274.427
• InChiKey: UWZGAQOHEQYREN-OLMNGRFOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.65
• 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：

  (1S,2R,5R,7S,9R)-10,10-Dimethyl-5-phenyl-4-oxa-6-thia-tricyclo[7.1.1.0^2,7]undecane 在 仲丁基锂 、 重水 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 反应 0.67h， 以100%的产率得到(1S,2R,5S,7S,9R)-5-deuterio-10,10-dimethyl-5-phenyl-4-oxa-6-thiatricyclo[7.1.1.02,7]undecane
  参考文献：
  名称：

  New 1,3-Oxathianes Derived from Myrtenal:  Synthesis and Reactivity

  摘要：

  2-Methyl- and 2-phenyl-substituted oxathianes derived from Myrtenal have been synthesized in satisfying yields. Lithiation of 2-methyl-substituted oxathiane could not be done, but lithiation of 2-phenyl-substituted and non-substituted oxathianes could be performed with s-BuLi. Quenching with D2O, TMSCl, and/or a carbonyl compound always provides the equatorial product in consistency with a prefered equatorial orientation of the lithium in the lithiated derivatives. A model is proposed to rationalize the diastereoselectivities observed at C5' during reaction of aldehydes with lithiated non-substituted oxathiane. The model is based on the hypothesis that the lithium, being-linked simultaneously to the carbon and the oxygen, is shifted toward the oxygen side, making the steric hindrance of this side more effective. Dimeric side products were observed during formation of these oxathianes (condensation of various aldehydes with the corresponding hydroxythiol), which had not been reported for other oxathianes (derived from pulegone and/or camphorsulfonic,acid).

  DOI：

  10.1021/jo034404w
• 作为产物：
  描述：

  桃金娘烯醛 在 lithium aluminium tetrahydride 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙醚 、 苯 为溶剂， 反应 2.0h， 生成 (1S,2R,5R,7S,9R)-10,10-Dimethyl-5-phenyl-4-oxa-6-thia-tricyclo[7.1.1.0^2,7]undecane
  参考文献：
  名称：

  New 1,3-Oxathianes Derived from Myrtenal:  Synthesis and Reactivity

  摘要：

  2-Methyl- and 2-phenyl-substituted oxathianes derived from Myrtenal have been synthesized in satisfying yields. Lithiation of 2-methyl-substituted oxathiane could not be done, but lithiation of 2-phenyl-substituted and non-substituted oxathianes could be performed with s-BuLi. Quenching with D2O, TMSCl, and/or a carbonyl compound always provides the equatorial product in consistency with a prefered equatorial orientation of the lithium in the lithiated derivatives. A model is proposed to rationalize the diastereoselectivities observed at C5' during reaction of aldehydes with lithiated non-substituted oxathiane. The model is based on the hypothesis that the lithium, being-linked simultaneously to the carbon and the oxygen, is shifted toward the oxygen side, making the steric hindrance of this side more effective. Dimeric side products were observed during formation of these oxathianes (condensation of various aldehydes with the corresponding hydroxythiol), which had not been reported for other oxathianes (derived from pulegone and/or camphorsulfonic,acid).

  DOI：

  10.1021/jo034404w

文献信息

• New 1,3-Oxathianes Derived from Myrtenal:  Synthesis and Reactivity
  作者：Arlette Solladié-Cavallo、Milan Balaz、Marta Salisova、Richard Welter

  DOI：10.1021/jo034404w

  日期：2003.8.1

  2-Methyl- and 2-phenyl-substituted oxathianes derived from Myrtenal have been synthesized in satisfying yields. Lithiation of 2-methyl-substituted oxathiane could not be done, but lithiation of 2-phenyl-substituted and non-substituted oxathianes could be performed with s-BuLi. Quenching with D2O, TMSCl, and/or a carbonyl compound always provides the equatorial product in consistency with a prefered equatorial orientation of the lithium in the lithiated derivatives. A model is proposed to rationalize the diastereoselectivities observed at C5' during reaction of aldehydes with lithiated non-substituted oxathiane. The model is based on the hypothesis that the lithium, being-linked simultaneously to the carbon and the oxygen, is shifted toward the oxygen side, making the steric hindrance of this side more effective. Dimeric side products were observed during formation of these oxathianes (condensation of various aldehydes with the corresponding hydroxythiol), which had not been reported for other oxathianes (derived from pulegone and/or camphorsulfonic,acid).