(1R,10aR)-2-Benzyl 1-methyl 7-methoxy-1,9,10,10a-tetrahydrophenanthrene-1,2-dicarboxylate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: (1R,10aR)-2-Benzyl 1-methyl 7-methoxy-1,9,10,10a-tetrahydrophenanthrene-1,2-dicarboxylate
• 英文别名: 2-O-benzyl 1-O-methyl (1R,10aR)-7-methoxy-1,9,10,10a-tetrahydrophenanthrene-1,2-dicarboxylate
• 化学式: C₂₅H₂₄O₅
• 分子量: 404.463
• InChiKey: BQQAWJXMGCHWLW-JTHBVZDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  7-甲氧基-4-乙烯基-1,2-二氢萘 、 (S)-1-Benzyl 4-methyl 2-p-tolylsulfinylmaleate 在 Eu(fod)3 作用下， 生成 (1R,10aS)-2-Benzyl 1-methyl 7-methoxy-1,9,10,10a-tetrahydrophenanthrene-1,2-dicarboxylate 、 (1R,10aR)-2-Benzyl 1-methyl 7-methoxy-1,9,10,10a-tetrahydrophenanthrene-1,2-dicarboxylate
  参考文献：
  名称：

  Benzyl Methyl (S)-2-(p-Tolylsulfinyl)maleate, an Efficient Dienophile in Asymmetric Diels-Alder Reactions

  摘要：

  The enantiomerically pure dienophile 3 [1-benzyl 4-methyl (S)-(p-tolylsulfinyl)maleate] was readily prepared in a three-step sequence from benzyl acetate and (-)-(S)-menthyl p-toluenesulfinate (46% overall yield). This vinyl sulfoxide reacted in high yields and with very high regioselectivities and stereoselectivities with a wide variety of 1,3-dienes (10 examples) at low temperature in the presence of Eu(fod)3 or TiCl4. Whereas cycloadditions catalyzed by TiCl4 (usually carried out at -78-degrees-C) occurred with complete regioselectivity, endo selectivity, and pi-facial selectivity, the cycloaddition catalyzed by Eu(fod)3 (usually performed at 0-degrees-C) also occurred with very high regioselectivity and pi-facial selectivity, but with low endo selectivity. Interestingly, all the adducts (excepting the adducts from cyclopentadiene) are unstable at room temperature, undergoing spontaneous sulfinyl elimination to give 1,3-cyclohexadienes 7 and/or 1,4-cyclohexadienes 11, in excellent yields. Regardless of the catalyst, compounds 7 showed a very high optical purity (ee greater-than-or-equal-to 96%). Finally, some models based on the conformational equilibrium of vinyl sulfoxide 3 have been proposed to explain the observed stereoselectivities.

  DOI：

  10.1021/jo00085a043

文献信息

• Benzyl Methyl (S)-2-(p-Tolylsulfinyl)maleate, an Efficient Dienophile in Asymmetric Diels-Alder Reactions
  作者：Ines Alonso、Juan C. Carretero、Jose L. Garcia Ruano

  DOI：10.1021/jo00085a043

  日期：1994.3

  The enantiomerically pure dienophile 3 [1-benzyl 4-methyl (S)-(p-tolylsulfinyl)maleate] was readily prepared in a three-step sequence from benzyl acetate and (-)-(S)-menthyl p-toluenesulfinate (46% overall yield). This vinyl sulfoxide reacted in high yields and with very high regioselectivities and stereoselectivities with a wide variety of 1,3-dienes (10 examples) at low temperature in the presence of Eu(fod)3 or TiCl4. Whereas cycloadditions catalyzed by TiCl4 (usually carried out at -78-degrees-C) occurred with complete regioselectivity, endo selectivity, and pi-facial selectivity, the cycloaddition catalyzed by Eu(fod)3 (usually performed at 0-degrees-C) also occurred with very high regioselectivity and pi-facial selectivity, but with low endo selectivity. Interestingly, all the adducts (excepting the adducts from cyclopentadiene) are unstable at room temperature, undergoing spontaneous sulfinyl elimination to give 1,3-cyclohexadienes 7 and/or 1,4-cyclohexadienes 11, in excellent yields. Regardless of the catalyst, compounds 7 showed a very high optical purity (ee greater-than-or-equal-to 96%). Finally, some models based on the conformational equilibrium of vinyl sulfoxide 3 have been proposed to explain the observed stereoselectivities.