(+)-(S)-2-(hydroxymethyl)-2-hydroxycyclohexanone acetonide | 143076-43-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-(S)-2-(hydroxymethyl)-2-hydroxycyclohexanone acetonide
• 英文别名: (5S)-2,2-dimethyl-1,3-dioxaspiro[4.5]decan-6-one
• CAS: 143076-43-1
• 化学式: C₁₀H₁₆O₃
• 分子量: 184.235
• InChiKey: FOZXPQCIWHSUBX-JTQLQIEISA-N

物化性质

• 沸点：
  270.4±30.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-(S)-2-(hydroxymethyl)-2-hydroxycyclohexanone acetonide 在 四(三苯基膦)钯 lithium chloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 26.5h， 生成 1,3-Dioxaspiro[4.5]dec-6-ene, 6-ethenyl-2,2-dimethyl-, (R)-
  参考文献：
  名称：

  Asymmetric synthesis of tanshindiol A.

  摘要：

  The ultrasound-promoted Diels-Alder reaction of 3-methyl-4,5-benzofurandione (10) with appropriately substituted vinylcyclohexenes has led to the synthesis of tanshindiol A (9), a minor component of the Chinese traditional medicine, Dan Shen, prepared from the roots of Salvia miltiorrhiza Bunge. The regioselectivity of the cycloaddition was enhanced by the ultrasonication and was also strongly influenced by the solvent. The asymmetric synthesis of (+)-(4R)-tanshindiol A [(+)-(4R)-91, the naturally occurring enantiomer, proceeded from the optically enriched methyl 6-(benzoyloxy)-1-vinylcyclohexene-6-carboxylate [(-)-(R)-15] or 6-hydroxy-6-(hydroxymethyl)-l-vinylcyclohexene acetonide [(+)-(R)-291 (both 92% ee). Enantioselectivity in the preparation of these diene systems was accomplished by the benzoyl peroxide quench of the lithioenamine derived from methyl 1-oxocyclohexane-2-carboxylate and (S)-valine tert-butyl ester. This procedure, adapted from Koga's asymmetric alkylation of alpha-alkyl beta-keto esters, proved highly effective in preparing the necessary tertiary alcohol in protected form and with high optical purity.

  DOI：

  10.1021/jo00046a009
• 作为产物：
  描述：

  1-<<(tert-butyldimethylsilyl)oxy>methyl>cyclohexane-1,2-diol 在 重铬酸吡啶 、 D(+)-10-樟脑磺酸 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 32.33h， 生成 (+)-(S)-2-(hydroxymethyl)-2-hydroxycyclohexanone acetonide
  参考文献：
  名称：

  Asymmetric synthesis of tanshindiol A.

  摘要：

  The ultrasound-promoted Diels-Alder reaction of 3-methyl-4,5-benzofurandione (10) with appropriately substituted vinylcyclohexenes has led to the synthesis of tanshindiol A (9), a minor component of the Chinese traditional medicine, Dan Shen, prepared from the roots of Salvia miltiorrhiza Bunge. The regioselectivity of the cycloaddition was enhanced by the ultrasonication and was also strongly influenced by the solvent. The asymmetric synthesis of (+)-(4R)-tanshindiol A [(+)-(4R)-91, the naturally occurring enantiomer, proceeded from the optically enriched methyl 6-(benzoyloxy)-1-vinylcyclohexene-6-carboxylate [(-)-(R)-15] or 6-hydroxy-6-(hydroxymethyl)-l-vinylcyclohexene acetonide [(+)-(R)-291 (both 92% ee). Enantioselectivity in the preparation of these diene systems was accomplished by the benzoyl peroxide quench of the lithioenamine derived from methyl 1-oxocyclohexane-2-carboxylate and (S)-valine tert-butyl ester. This procedure, adapted from Koga's asymmetric alkylation of alpha-alkyl beta-keto esters, proved highly effective in preparing the necessary tertiary alcohol in protected form and with high optical purity.

  DOI：

  10.1021/jo00046a009

文献信息

• Stereocontrolled Synthesis of Oxaspirobicycles <i>via</i> Prins-Pinacol Annulation
  作者：Satish N Chavre、Punna Reddy Ullapu、Sun-Joon Min、Jae Kyun Lee、Ae Nim Pae、Youseung Kim、Yong Seo Cho

  DOI：10.1021/ol9014078

  日期：2009.9.3

  We have developed the stereoselective synthesis of 2-oxaspiro[m,n]alkane derivatives using the Prins-pinacol annulation of alkene diols with a wide range of aliphatic or aromatic aldehydes and ketones. This approach was further applied for the synthesis of oxatricyclic ring system.

  我们已经开发了使用具有多种脂族或芳族醛和酮的链烯二醇的Prins-频哪醇环化技术，对2-oxaspiro [ m，n ]烷烃衍生物进行立体选择性合成。该方法被进一步应用于乙三环系统的合成。
• Asymmetric synthesis of tanshindiol A.
  作者：Junning Lee、Jiahe Li、Shunichi Oya、John K. Snyder

  DOI：10.1021/jo00046a009

  日期：1992.9

  The ultrasound-promoted Diels-Alder reaction of 3-methyl-4,5-benzofurandione (10) with appropriately substituted vinylcyclohexenes has led to the synthesis of tanshindiol A (9), a minor component of the Chinese traditional medicine, Dan Shen, prepared from the roots of Salvia miltiorrhiza Bunge. The regioselectivity of the cycloaddition was enhanced by the ultrasonication and was also strongly influenced by the solvent. The asymmetric synthesis of (+)-(4R)-tanshindiol A [(+)-(4R)-91, the naturally occurring enantiomer, proceeded from the optically enriched methyl 6-(benzoyloxy)-1-vinylcyclohexene-6-carboxylate [(-)-(R)-15] or 6-hydroxy-6-(hydroxymethyl)-l-vinylcyclohexene acetonide [(+)-(R)-291 (both 92% ee). Enantioselectivity in the preparation of these diene systems was accomplished by the benzoyl peroxide quench of the lithioenamine derived from methyl 1-oxocyclohexane-2-carboxylate and (S)-valine tert-butyl ester. This procedure, adapted from Koga's asymmetric alkylation of alpha-alkyl beta-keto esters, proved highly effective in preparing the necessary tertiary alcohol in protected form and with high optical purity.