(1S,2R,5R,7S,9R)-5-benzoyl-10,10-dimethyl-4-oxa-6-thiatricyclo[7.1.1.0^2,7]undecane | 599192-45-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2R,5R,7S,9R)-5-benzoyl-10,10-dimethyl-4-oxa-6-thiatricyclo[7.1.1.0^2,7]undecane
• 英文别名: [(1S,2R,5R,7S,9R)-10,10-dimethyl-4-oxa-6-thiatricyclo[7.1.1.02,7]undecan-5-yl]-phenylmethanone
• CAS: 599192-45-7
• 化学式: C₁₈H₂₂O₂S
• 分子量: 302.437
• InChiKey: MIKOUZOVESQRHE-JLHDYFKBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.61
• 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：

  (1S,2R,5R,7S,9R)-5-benzoyl-10,10-dimethyl-4-oxa-6-thiatricyclo[7.1.1.0^2,7]undecane 在 N-氯代丁二酰亚胺 、 lithium aluminium tetrahydride 、 silver nitrate 作用下， 以 四氢呋喃 、 水 、 乙腈 为溶剂， 生成 10-hydroxyisopinocampheylthiol
  参考文献：
  名称：

  Enantioselective synthesis of either enantiomer of α-alkyl-α-hydroxy-α-phenylacetic acids using chiral auxiliaries

  摘要：

  The enantioselective synthesis of either enantiomer of of alpha-alkyl-alpha-hydroxy-alpha-phenylacetic acids was achieved by using 2-acyloxathianes 1a-c and the mixed acyl-S,O-acetals 7 and 8 as chiral auxiliaries, which can straightforwardly be prepared from (1R)-(-)-myrtenal. This procedure allowed the preparation of the title compounds in >95% enantiomeric excess (ee). (C) 2005 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetasy.2005.03.032
• 作为产物：
  描述：

  10-hydroxyisopinocampheylthiol 在 对甲苯磺酸 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 反应 1.0h， 生成 (1S,2R,5R,7S,9R)-5-benzoyl-10,10-dimethyl-4-oxa-6-thiatricyclo[7.1.1.0^2,7]undecane
  参考文献：
  名称：

  New S,O-acetals from (1R)-(−)-myrtenal as chiral auxiliaries in nucleophilic additions

  摘要：

  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.

  DOI：

  10.1016/j.tetlet.2004.01.046

文献信息

• Enantioselective synthesis of 1-alkyl-substituted 1-phenyl-1,2-ethanediols using a myrtenal-derived chiral auxiliary
  作者：Marı́a Elena Vargas-Dı́az、Luis Chacón-Garcı́a、Pedro Velázquez、Joaquı́n Tamariz、Pedro Joseph-Nathan、L.Gerardo Zepeda

  DOI：10.1016/j.tetasy.2003.07.017

  日期：2003.10

  The enantioselective synthesis of several 1-phenyl-1,2-ethanodiol derivatives using 2-benzoyl-1,3-oxathiane 1 as a chiral auxiliary is described. Nucleophilic additions of Grignard reagents, methyl lithium and LS-Selectride on benzoyloxathiane 1 proceeded in >95% diastereomeric ratio (dr) affording the corresponding tertiary carbinols, which were successively hydrolyzed and reduced to give the title derivatives in >95% enantiomeric excess (ee). (C) 2003 Elsevier 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).
• 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.
• Enantioselective synthesis of either enantiomer of α-alkyl-α-hydroxy-α-phenylacetic acids using chiral auxiliaries
  作者：Salvador Pérez-Estrada、Selene Lagunas-Rivera、Marı́a Elena Vargas-Dı́az、Pedro Velázquez-Ponce、Pedro Joseph-Nathan、L. Gerardo Zepeda

  DOI：10.1016/j.tetasy.2005.03.032

  日期：2005.5

  The enantioselective synthesis of either enantiomer of of alpha-alkyl-alpha-hydroxy-alpha-phenylacetic acids was achieved by using 2-acyloxathianes 1a-c and the mixed acyl-S,O-acetals 7 and 8 as chiral auxiliaries, which can straightforwardly be prepared from (1R)-(-)-myrtenal. This procedure allowed the preparation of the title compounds in >95% enantiomeric excess (ee). (C) 2005 Published by Elsevier Ltd.