(1S,2R,8R,9S,11R,13S,17S,19R)-10,10,20,20-tetramethyl-4,6-dioxa-14,16-dithiapentacyclo[17.1.1.19,11.02,17.08,13]docosane | 599192-52-6

• 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,8R,9S,11R,13S,17S,19R)-10,10,20,20-tetramethyl-4,6-dioxa-14,16-dithiapentacyclo[17.1.1.19,11.02,17.08,13]docosane
• CAS: 599192-52-6
• 化学式: C₂₂H₃₆O₂S₂
• 分子量: 396.659
• InChiKey: QRVJNSHOHNNOJO-GSDNACIXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  69.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,2R,8R,9S,11R,13S,17S,19R)-10,10,20,20-tetramethyl-4,6-dioxa-14,16-dithiapentacyclo[17.1.1.19,11.02,17.08,13]docosane 在 sodium periodate 、 双氧水 作用下， 以 乙醇 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  Efficient and highly diastereoselective preparation of a myrtenal derived bis-sulfoxide and its preliminary evaluation as chiral acyl donor

  摘要：

  Treatment of disulfide 7 with NalO(4) in EtOH at rt gave monosulfoxide 8 (95YO), while at 50 degrees C it gave trans-bis-sulfoxide 6a (84%, > 99% de). In contrast, treatment of 7 with MCPBA gave bis-sulfone 9 (95%). The anion of 6a reacted with benzaldehyde affording carbinol 10 (76%, > 99%, de). The absolute configuration of 8, 6a, and 10 was established by single crystal X-ray diffraction analyses. (c) 2005 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetlet.2005.03.104
• 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 0.5h， 生成 (1S,2R,8R,9S,11R,13S,17S,19R)-10,10,20,20-tetramethyl-4,6-dioxa-14,16-dithiapentacyclo[17.1.1.19,11.02,17.08,13]docosane
  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

• Synthesis of a New (1<i>R</i>)-(−)-Myrtenal-Derived Dioxadithiadodecacycle and Its Use as an Efficient Chiral Auxiliary
  作者：M. Elena Vargas-Díaz、Pedro Joseph-Nathan、Joaquín Tamariz、L. Gerardo Zepeda

  DOI：10.1021/ol062319f

  日期：2007.1.1

  [reaction: see text] The new macrocycle 9 (>70% yield from hydroxythiol 10) was treated with several nucleophilic reagents (RMgX, RLi, and LiAlH4) affording carbinols 12a-j (80-96% yield, >99:1 dr). Oxidative hydrolysis of 12a,c,e, followed by LiAlH4 reduction of the resulting mixture, gave 16a,c,e in >95% ee,16c being a key precursor for the preparation of fungicide 17. The absolute configuration

  [反应：请参见文本]用几种亲核试剂（RMgX，RLi和LiAlH4）处理了新的大环化合物9（羟基硫醇10的产率> 70％），得到甲醇12a-j（产率80-96％，> 99：1 dr ）。12a，c，e的氧化水解，然后将所得混合物进行LiAlH4还原，得到> 95％ee，16c的16a，c，e，这是制备杀菌剂17的关键前体。9和12j的绝对构型（ Nu = H）是通过单晶X射线衍射分析和化学相关性建立的。
• 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.
• Efficient and highly diastereoselective preparation of a myrtenal derived bis-sulfoxide and its preliminary evaluation as chiral acyl donor
  作者：M. Elena Vargas-Dı́az、Selene Lagunas-Rivera、Pedro Joseph-Nathan、Joaquı́n Tamariz、L. Gerardo Zepeda

  DOI：10.1016/j.tetlet.2005.03.104

  日期：2005.5

  Treatment of disulfide 7 with NalO(4) in EtOH at rt gave monosulfoxide 8 (95YO), while at 50 degrees C it gave trans-bis-sulfoxide 6a (84%, > 99% de). In contrast, treatment of 7 with MCPBA gave bis-sulfone 9 (95%). The anion of 6a reacted with benzaldehyde affording carbinol 10 (76%, > 99%, de). The absolute configuration of 8, 6a, and 10 was established by single crystal X-ray diffraction analyses. (c) 2005 Published by Elsevier Ltd.
• 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).