(S)-1-Benzyl 4-methyl 2-p-tolylsulfinylmaleate | 148871-72-1

• 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: (S)-1-Benzyl 4-methyl 2-p-tolylsulfinylmaleate
• 英文别名: Benzyl methyl (S)-2-(p-tolylsulfinyl)maleate；1-O-benzyl 4-O-methyl (E)-2-[(S)-(4-methylphenyl)sulfinyl]but-2-enedioate
• CAS: 148871-72-1
• 化学式: C₁₉H₁₈O₅S
• 分子量: 358.415
• InChiKey: RUXNBYQSLGWDEN-GCTXXEFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  88.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (S)-1-Benzyl 4-methyl 2-p-tolylsulfinylmaleate 在 zinc dibromide 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 6.0h， 生成 (+)-(1S,4R)-2-Benzyl 3-methyl bicyclo<2.2.1>hepta-2,5-diene-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
• 作为产物：
  描述：

  乙酸苄酯 在 四氢吡咯 、 bromomagnesium diisopropylamide 、 4 A molecular sieve 、 碳酸氢钠 、 三乙胺 作用下， 以 乙醚 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 13.0h， 生成 (S)-1-Benzyl 4-methyl 2-p-tolylsulfinylmaleate
  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 for the enantioselective synthesis of cyclohexadienes
  作者：Ines Alonso、Juan C. Carretero、Jose L. Garcia Ruano

  DOI：10.1021/jo00064a005

  日期：1993.6

  The new dienophile, benzyl methyl (S)-2-(p-tolylsulfinyl)maleate, readily prepared in two steps from benzyl acetate, reacts with a wide variety of 1,3-dienes, under catalysis by TiC4, in a very regioselective and stereoselective manner to give optically pure (ee >96%) 1,3- and/or 1,4-cyclohexadienedicarboxylate esters in very high yields.
• A highly enantioselective approach to functionalized [4.n.0] bicyclic compounds
  作者：Juan C Carretero、José L García Ruano、Luisa M Martín Cabrejas

  DOI：10.1016/s0040-4039(00)78213-x

  日期：1994.8

  The Diels-Alder reaction of benzyl, methyl (S)-2-(p-tolylsulfinyl) maleate with several 1-vinylcycloalkenes, catalyzed by TiCl4, occurred with complete regio and stereoselectivity. The regioselectivity of the sulfinyl elimination from the adducts, as well as;the stereoselectivity of the epoxidation and the hydroboration of the resulting [4.n.0] bicyclic compounds, increase with the size of the second ring.