(S₁,S₂,R₃,R₄,S_S)-2-Benzyl 3-methyl 2-p-(tolylsulfinyl)bicyclo<2.2.1>hept-5-ene-2,3-dicarboxylate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S₁,S₂,R₃,R₄,S_S)-2-Benzyl 3-methyl 2-p-(tolylsulfinyl)bicyclo<2.2.1>hept-5-ene-2,3-dicarboxylate
• 英文别名: (S₁,S₂,R₃,R₄,S_S)-2-Benzyl 3-methyl 2-p-(tolylsulfinyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate；2-O-benzyl 3-O-methyl (1S,2S,3R,4R)-2-[(S)-(4-methylphenyl)sulfinyl]bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate
• 化学式: C₂₄H₂₄O₅S
• 分子量: 424.518
• InChiKey: OFILYRXWPLIAFG-LMASNEEKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  88.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  乙酸苄酯 在 zinc dibromide 四氢吡咯 、 bromomagnesium diisopropylamide 、 4 A molecular sieve 、 碳酸氢钠 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 19.0h， 生成 (S₁,S₂,R₃,R₄,S_S)-2-Benzyl 3-methyl 2-p-(tolylsulfinyl)bicyclo<2.2.1>hept-5-ene-2,3-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.