(5R)-5-ethoxy-4-methyl-3-((S)-p-tolylsulfinyl)furan-2(5H)-one | 181378-65-4

• 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: (5R)-5-ethoxy-4-methyl-3-((S)-p-tolylsulfinyl)furan-2(5H)-one
• 英文别名: (2R)-2-ethoxy-3-methyl-4-[(S)-(4-methylphenyl)sulfinyl]-2H-furan-5-one
• CAS: 181378-65-4
• 化学式: C₁₄H₁₆O₄S
• 分子量: 280.345
• InChiKey: AKMYJIXEZYNWRB-KUHUBIRLSA-N

物化性质

• 沸点：
  536.3±50.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  71.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (5R)-5-ethoxy-4-methyl-3-((S)-p-tolylsulfinyl)furan-2(5H)-one 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 8.5h， 以88%的产率得到(1R,4R,5S)-4-ethoxy-5-methyl-1-p-tolylsulfonyl-3,6-dioxabicyclo[3.1.0]hexan-2-one
  参考文献：
  名称：

  4-乙氧基-1-对甲苯磺酰基-3,6-二氧杂双环[3.1.0]己-2-基的不对称合成

  摘要：

  通过在室温下用MCPBA处理，光学纯的亚磺酰基呋喃酮在硫上进行氧化，然后在缺电子的双键上进行完全立体选择性环氧化，以良好的收率得到对映体纯的4-乙氧基-5-烷基-1-对甲苯磺酰基-3 ，6-二氧杂双环[3.1.0]己-2-酮。这些环氧呋喃酮与环丙烷呋喃酮通过4-乙氧基-6-对甲苯磺酰基呋喃[3,4-c]吡唑啉-6-酮与MPCBA的反应获得。在这两种情况下，磺酰环氧内酯的形成都是通过磺酰呋喃-2（5 H）-一种由起始材料产生的结果。该反应是完全立体选择性的（受呋喃酮的C-5构型控制），是由于试剂与底物上弱碱性中心的相互作用所产生的过氧羧酸盐的亲核攻击所致。

  DOI：

  10.1016/j.tet.2009.10.106
• 作为产物：
  描述：

  (R₅,S_S)-5-ethoxy-3-(p-tolylsulfinyl)furan-2(5H)-one 以 乙醚 、 甲苯 为溶剂， 反应 3.08h， 生成 (5R)-5-ethoxy-4-methyl-3-((S)-p-tolylsulfinyl)furan-2(5H)-one
  参考文献：
  名称：

  （S s）-5-乙氧基-3-对甲苯基亚磺酰基呋喃-2（5 H）-手性偶极亲和剂：重氮甲烷与乙烯基亚砜的第一次不对称环加成

  摘要：

  重氮甲烷与（S s）-5-乙氧基-3-对甲苯磺酰呋喃-2（5 H）-ones 1a–b及其相应的4-甲基衍生物3a–b的环加成反应以定量产率进行，得到对映体纯的3 H，6 H，3a，6a-二氢呋喃[3,4-c]吡唑-4-酮2a–b和4a–b。C-3处的亚磺酰基会大大提高反应性和π面选择性。偶极接近模式由亚磺酰基的构型决定。吡唑啉2a或2b的热解得到甲基衍生物3a或3b的产量极高。

  DOI：

  10.1016/0957-4166(96)00233-9

文献信息

• The Role of Steric and Electronic Interactions in the Stereocontrol of the Asymmetric 1,3-Dipolar Reactions of 5-Ethoxy-3-<i>p</i>-(<i>S</i>)-tolylsulfinylfuran-2(5<i>H</i>)-ones with Diazoalkanes:  Theoretical Calculations and Experimental Evidences
  作者：José L. García Ruano、Alberto Fraile、Gemma González、M. Rosario Martín、Fernando R. Clemente、Ruth Gordillo

  DOI：10.1021/jo0345603

  日期：2003.8.1

  The addition of diazomethane and diazoethane to (5S,SS)- and (5R,SS)-5-ethoxy-3-p-tolylsulfinylfuran-2(5H)-ones (1a and 1B) and their 4-methylderivatives (2a and 2b) proceeded in almost quantitative yields and complete regioselectivity. The observed pi-facial selectivity is determined by the configurations at both C-5 and the sulfinyl group, the later being the most important. The syn adducts were almost exclusively obtained from 1a and 2a in apolar solvents but the pi-facial selectivity was strongly decreased in more polar solvents. On the other hand, the major adducts from 1b and 2b were the anti ones and such predominance was slightly increased with solvent polarity. The exo-selectivity was complete in all the cases except for the anti approach to compounds 2a (in polar solvents) and 2b. The role of the sulfinyl group in this behavior was inferred by comparison of these results with those obtained in reactions of diazoalkanes with 5-methoxyfuran-2(5H)-one (3). Steric interactions seem to be the main ones responsible for the observed exo selectivity of reactions with diazoethane, but electronic factors, which can be modulated by the solvent, are also significant in the pi-facial selectivity control. DFT computational methods are able to correctly predict the reactivity, regioselectivity, and pi-facial selectivity exhibited by 5-alkoxy-furanones as well as their changes with the solvent polarity. A C-H...O hydrogen bond, involving the oxygen atom of the 5-alkoxy group at dipolarophiles and the endo-hydrogen atom at dipoles, seems to play a key role in the electronic interactions influencing the stereochemical course of these reactions.
• Asymmetric synthesis of 4-ethoxy-1-p-tolylsulfonyl-3,6-dioxabicyclo[3.1.0]hexan-2-ones
  作者：Alberto Fraile、José Luis García Ruano、M. Rosario Martín、Amelia Tito

  DOI：10.1016/j.tet.2009.10.106

  日期：2010.1

  epoxidation at the electron deficient double bond by treatment with MCPBA at room temperature to afford, in good yields, enantiomerically pure 4-ethoxy-5-alkyl-1-p-tolylsulfonyl-3,6-dioxabicyclo[3.1.0]hexan-2-ones. These epoxyfuranones are obtained along with cyclopropanefuranones by reaction of 4-ethoxy-6-p-tolylsulfinylfuro[3,4-c]pyrazolin-6-ones with MPCBA. In both cases, the formation of the sulfonyl

  通过在室温下用MCPBA处理，光学纯的亚磺酰基呋喃酮在硫上进行氧化，然后在缺电子的双键上进行完全立体选择性环氧化，以良好的收率得到对映体纯的4-乙氧基-5-烷基-1-对甲苯磺酰基-3 ，6-二氧杂双环[3.1.0]己-2-酮。这些环氧呋喃酮与环丙烷呋喃酮通过4-乙氧基-6-对甲苯磺酰基呋喃[3,4-c]吡唑啉-6-酮与MPCBA的反应获得。在这两种情况下，磺酰环氧内酯的形成都是通过磺酰呋喃-2（5 H）-一种由起始材料产生的结果。该反应是完全立体选择性的（受呋喃酮的C-5构型控制），是由于试剂与底物上弱碱性中心的相互作用所产生的过氧羧酸盐的亲核攻击所致。
• (Ss)-5-ethoxy-3-p-tolylsulfinylfuran-2(5H)-ones as chiral dipolarophiles: First asymmetric cycloaddition of diazomethane to vinyl sulfoxides
  作者：Jose L. García Ruano、Alberto Fraile、M. Rosario Martín

  DOI：10.1016/0957-4166(96)00233-9

  日期：1996.7

  Cycloadditions of diazomethane to (Ss)-5-ethoxy-3-p-tolylsulfinylfuran-2(5H)-ones 1a–b and their corresponding 4-methyl derivatives 3a–b, proceeds in quantitative yields, to give enantiomerically pure 3H,6H,3a,6a-dihydrofuro[3,4-c]pyrazol-4-ones 2a–b and 4a–b, respectively. The sulfinyl group at C-3 strongly increases both the reactivity and the π-facial selectivity. The dipole approach mode is determined

  重氮甲烷与（S s）-5-乙氧基-3-对甲苯磺酰呋喃-2（5 H）-ones 1a–b及其相应的4-甲基衍生物3a–b的环加成反应以定量产率进行，得到对映体纯的3 H，6 H，3a，6a-二氢呋喃[3,4-c]吡唑-4-酮2a–b和4a–b。C-3处的亚磺酰基会大大提高反应性和π面选择性。偶极接近模式由亚磺酰基的构型决定。吡唑啉2a或2b的热解得到甲基衍生物3a或3b的产量极高。