(1S,2R,7S)-10,10-dimethyl-4-oxa-6-thiatricyclo[7.1.1.0^2,7]undecane | 444308-39-8

• 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,7S)-10,10-dimethyl-4-oxa-6-thiatricyclo[7.1.1.0^2,7]undecane
• 英文别名: (1S,2R,7S,9R)-10,10-dimethyl-4-oxa-6-thiatricyclo[7.1.1.02,7]undecane
• CAS: 444308-39-8
• 化学式: C₁₁H₁₈OS
• 分子量: 198.329
• InChiKey: VMASDBDXESTRBL-KATARQTJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 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,7S)-10,10-dimethyl-4-oxa-6-thiatricyclo[7.1.1.0^2,7]undecane 在 lithium aluminium tetrahydride 、 仲丁基锂 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 反应 3.42h， 生成 (1S,2R,5R,7S,9R)-5-[(R)-(hydroxy)(phenyl)methyl]-10,10-dimethyl-4-oxa-6-thiatricyclo[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
• 作为产物：
  描述：

  (1S,2R,3S)-2-hyroxymethyl-6,6-dimethyl-3-thiobenzylbicyclo[3.1.1]heptane 在 sodium 、 对甲苯磺酸 作用下， 以 乙醚 、 氨 、 甲苯 为溶剂， 反应 4.0h， 生成 (1S,2R,7S)-10,10-dimethyl-4-oxa-6-thiatricyclo[7.1.1.0^2,7]undecane
  参考文献：
  名称：

  Highly diastereoselective nucleophilic additions using a novel myrtenal-derived oxathiane as a chiral auxiliary

  摘要：

  The synthesis of novel oxathiane 3 and its acetyl derivative 12, from commercially available (-)myrtenal 4, is described. The addition of several nucleophilic reagents to 12 furnished the corresponding tertiary carbinols in highly diastereomeric excess. The hydrolysis of 11a, b yielded the expected alpha-hydroxycarbonyl compounds in excellent enantiomeric excess. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00545-6

文献信息

• New S,O-acetals from (1R)-(−)-myrtenal as chiral auxiliaries in nucleophilic additions
  作者：Luis Chacón-Garcı́a、Selene Lagunas-Rivera、Salvador Pérez-Estrada、M. Elena Vargas-Dı́az、Pedro Joseph-Nathan、Joaquı́n Tamariz、L.Gerardo Zepeda

  DOI：10.1016/j.tetlet.2004.01.046

  日期：2004.3

  Treatment of hydroxythiol 4 with alpha,alpha-diethoxyacetophenone at room temperature yielded a mixture of epimeric S,O-acetals 6 and 7 (1:4. 92%, yield), which were efficiently separated by flash chromatography. The OTBS derivatives 8 and 9 were treated with several Grignard reagents to afford carbinols 10 and 13 respectively (85-99%, yield, >95% dr). After successive hydrolysis and reduction of 10 and 13 it is possible to obtain either enantiomer of diols 16 in high optical purity (>95% er). (C) 2004 Elsevier Ltd. All rights reserved.
• Highly diastereoselective nucleophilic additions using a novel myrtenal-derived oxathiane as a chiral auxiliary
  作者：Federico Martı́nez-Ramos、Marı́a Elena Vargas-Dı́az、Luis Chacón-Garcı́a、Joaquı́n Tamariz、Pedro Joseph-Nathan、L.Gerardo Zepeda

  DOI：10.1016/s0957-4166(01)00545-6

  日期：2001.12

  The synthesis of novel oxathiane 3 and its acetyl derivative 12, from commercially available (-)myrtenal 4, is described. The addition of several nucleophilic reagents to 12 furnished the corresponding tertiary carbinols in highly diastereomeric excess. The hydrolysis of 11a, b yielded the expected alpha-hydroxycarbonyl compounds in excellent enantiomeric excess. (C) 2002 Elsevier Science Ltd. All rights reserved.
• 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).