benzyl (R)-(+)-(p-tolylsulfinyl)acetate | 148871-73-2

• 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: benzyl (R)-(+)-(p-tolylsulfinyl)acetate
• 英文别名: (+)-(R)-Benzyl p-tolylsulfinylacetate；(+)-(R)-benzyl p-tolylsulfinylacetete；benzyl 2-[(R)-(4-methylphenyl)sulfinyl]acetate
• CAS: 148871-73-2
• 化学式: C₁₆H₁₆O₃S
• 分子量: 288.367
• InChiKey: QSTFQRYGJYZNAB-HXUWFJFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  62.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  benzyl (R)-(+)-(p-tolylsulfinyl)acetate 在 calcium carbonate 、 碘甲烷 作用下， 以 水 、 乙腈 为溶剂， 反应 14.0h， 生成 Benzyl (s)-2-(p-tolylsulfinyl)acrylate
  参考文献：
  名称：

  Enantioselective synthesis of (+)-shikimic acid and (+)-5-epi-shikimic acid by asymmetric Diels-Alder reaction of (S)-α-sulfinylacrylates

  摘要：

  Enantiopure (S) benzyl and t-butyl 2-p-tolylsulfinylpropenoates (1 and 2) were readily prepared by Mannich condensation of (R) p-tolylsulfinylacetates (CH2O+Me2NH), followed by in situ nitrogen quaternization. These new chiral dienophiles reacted with furan at high pressures (4-13 Kbar) at rt to afford mainly a 2:1 mixture of both endo adducts (endo-B+endo-A). Enantiopure endo-4B and endo-4A were stereoselectively transformed into (+)-shikimic acid and (+)-5-epi-shikimic acid respectively, by dihydroxylation of the double bond, removal of the sulfinyl group, basic opening of the oxabicyclic skeleton and hydrolysis of the ester moiety. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00151-1
• 作为产物：
  描述：

  乙酸苄酯 、 (-)-menthyl p-toluenesulfinate 在 bromomagnesium diisopropylamide 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以67%的产率得到benzyl (R)-(+)-(p-tolylsulfinyl)acetate
  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

• Short and Practical Syntheses of (S)-(+)-3-(p-Tolylsulfinyl)furan-2(5H)-one and (S)-(+)-3-(p-Tolylsulfinyl)-5,6-dihydropyran-2-one
  作者：Francisco Yuste、José García Ruano、David Cruz Cruz、Angélica Hernández Linares、M. Martín

  DOI：10.1055/s-0028-1088008

  日期：2009.4

  (S)-(+)-3-(p-Tolylsulfinyl)furan-2(5H)-one and (S)-(+)-3-(p-tolylsulfinyl)-5,6-dihydropyran-2-one can be synthesized by a new and significantly improved method consisting of Knoevenagel condensation of benzyl (R)-(+)-(p-tolylsulfinyl)acetate with the tert-butyldimethylsilyl derivatives of 2-hydroxyacetaldehyde or 3-hydroxypropanal, followed by subsequent reactions of the resulting mixtures with hydrogen

  （S）-（+）-3-（对甲苯磺酰基）呋喃-2（5 H）-和（S）-（+）-3-（对甲苯磺酰基）-5,6-二氢吡喃-2-一可以通过新的且显着改进的方法合成，该方法包括将苄基（R）-（+）-（对甲苯磺酸亚砜基）乙酸酯与2-羟基乙醛或3-羟基丙醛的叔丁基二甲基甲硅烷基衍生物进行Knoevenagel缩合，然后进行下列反应在碳载钯和氯化醚醚存在下，将所得混合物与氢气混合。 不对称合成-手性助剂-亚砜-α，β-不饱和内酯-丁烯内酯
• A sulfinyl trialkoxycarbonyl ethene as a new enantiopure dienophile in asymmetric diels-alder reactions
  作者：Juan C. Carretero、José L. García Ruano、Luisa M. Martín Cabrejas

  DOI：10.1016/0040-4020(95)00443-c

  日期：1995.7

  The synthesis and the asymmetric Diels-Alder reactions of the enantiomerically pure (S)-p-tolylsulfinyl trialkoxycarbonyl ethene 3 with cyclic and acyclic dienes are reported. π-Facial selectivity and regioselectivity are very high in all studied cases. Reactions with cyclopentadiene exhibit moderated or high exo-selectivity, which disappears with acyclic dienes. The use of high pressure improves the

  报道了对映体纯的（S）-对甲苯亚磺酰基三烷氧基羰基乙烯3与环状和非环状二烯的合成和不对称Diels-Alder反应。在所有研究的案例中，π面选择性和区域选择性都很高。与环戊二烯的反应显示出中等或高的外向选择性，在无环二烯中消失。高压的使用改善了π-面部选择性，但是基本上不改变内-外选择性。
• 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.
• Enantioselective synthesis of (+)-shikimic acid and (+)-5-epi-shikimic acid by asymmetric Diels-Alder reaction of (S)-α-sulfinylacrylates
  作者：Javier Adrio、Juan C. Carretero、Jose L. García Ruano、Luisa M. Martín Cabrejas

  DOI：10.1016/s0957-4166(97)00151-1

  日期：1997.5

  Enantiopure (S) benzyl and t-butyl 2-p-tolylsulfinylpropenoates (1 and 2) were readily prepared by Mannich condensation of (R) p-tolylsulfinylacetates (CH2O+Me2NH), followed by in situ nitrogen quaternization. These new chiral dienophiles reacted with furan at high pressures (4-13 Kbar) at rt to afford mainly a 2:1 mixture of both endo adducts (endo-B+endo-A). Enantiopure endo-4B and endo-4A were stereoselectively transformed into (+)-shikimic acid and (+)-5-epi-shikimic acid respectively, by dihydroxylation of the double bond, removal of the sulfinyl group, basic opening of the oxabicyclic skeleton and hydrolysis of the ester moiety. (C) 1997 Elsevier Science Ltd.
• 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.