(4E)(2R,3S)-3-hydroxy-2-methyl-5-phenyl-1-(2-thioxo(1,3-thiazolidin-3-yl))pent-4-en-1-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: (4E)(2R,3S)-3-hydroxy-2-methyl-5-phenyl-1-(2-thioxo(1,3-thiazolidin-3-yl))pent-4-en-1-one
• 英文别名: (E,2R,3S)-3-hydroxy-2-methyl-5-phenyl-1-(2-sulfanylidene-1,3-thiazolidin-3-yl)pent-4-en-1-one
• 化学式: C₁₅H₁₇NO₂S₂
• 分子量: 307.437
• InChiKey: JZRFSZQBPNWNGV-HOVLTTNMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  97.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl potassium malonate 、 (4E)(2R,3S)-3-hydroxy-2-methyl-5-phenyl-1-(2-thioxo(1,3-thiazolidin-3-yl))pent-4-en-1-one 在 咪唑 、 magnesium chloride 作用下， 以 乙醇 为溶剂， 以61%的产率得到ethyl (E,4R,5S)-5-hydroxy-4-methyl-3-oxo-7-phenylhept-6-enoate
  参考文献：
  名称：

  Versatile Asymmetric Synthesis of the Kavalactones:  First Synthesis of (+)-Kavain

  摘要：

  Three asymmetric pathways to the kavalactones have been developed. The first method is chiral auxiliary-based and utilizes aldol reactions of N-acetyl thiazolidinethiones followed by a malonate displacement/decarboxylation reaction. The second approach uses the asymmetric catalytic Mukaiyama additions of dienolate nucleophile equivalents developed by Carreira and Sato. Finally, tin-substituted intermediates, prepared by either of these routes, can serve as advanced general precursors of kavalactone derivatives via Pd(0)-catalyzed Stille couplings with aryl halides.

  DOI：

  10.1021/ol0493960
• 作为产物：
  描述：

  1-(2-硫酮-3-噻唑烷基)-1-丙酮 、 肉桂醛 在 2,6-二甲基吡啶 、 三氟甲磺酸三甲基硅酯 、 [Ni((S,S)-tert-butylbis(oxazoline)](OTf)2 、 盐酸 作用下， 以 二氯甲烷 、 甲苯 、 四氢呋喃 为溶剂， 生成 (4E)(2R,3S)-3-hydroxy-2-methyl-5-phenyl-1-(2-thioxo(1,3-thiazolidin-3-yl))pent-4-en-1-one 、 (4E)(2S,3R)-3-hydroxy-2-methyl-5-phenyl-1-(2-thioxo(1,3-thiazolidin-3-yl))pent-4-en-1-one 、 (2SR,3SR)-(4E)-3-hydroxy-2-methyl-5-phenyl-1-(2-thioxo(1,3-thiazolidin-3-yl))pent-4-en-1-one
  参考文献：
  名称：

  Ni(II)双(恶唑啉)-催化N-丙酰基噻唑烷硫酮在甲硅烷基三氟甲磺酸酯存在下的对映选择性合成羟醛反应

  摘要：

  公开了N-丙酰基噻唑烷硫酮和代表性醛的对映选择性羟醛反应。该反应由 [Ni(S,S)-t-BuBox](Otf)2 催化。烯醇化受 2,6-二甲基吡啶影响，TMSOTf 促进催化剂周转。合成非对映选择性范围为 88:12 至 97:3，对映选择性为 90% 或更高。芳香族和可烯醇化的脂肪族醛都包括在该醛醇加成过程的范围内。

  DOI：

  10.1021/ja035509j

文献信息

• Versatile Asymmetric Synthesis of the Kavalactones:  First Synthesis of (+)-Kavain
  作者：Thomas E. Smith、Mabel Djang、Alan J. Velander、C. Wade Downey、Kathleen A. Carroll、Sophie van Alphen

  DOI：10.1021/ol0493960

  日期：2004.7.1

  Three asymmetric pathways to the kavalactones have been developed. The first method is chiral auxiliary-based and utilizes aldol reactions of N-acetyl thiazolidinethiones followed by a malonate displacement/decarboxylation reaction. The second approach uses the asymmetric catalytic Mukaiyama additions of dienolate nucleophile equivalents developed by Carreira and Sato. Finally, tin-substituted intermediates, prepared by either of these routes, can serve as advanced general precursors of kavalactone derivatives via Pd(0)-catalyzed Stille couplings with aryl halides.
• Ni(II) Bis(oxazoline)-Catalyzed Enantioselective Syn Aldol Reactions of <i>N</i>-Propionylthiazolidinethiones in the Presence of Silyl Triflates
  作者：David A. Evans、C. Wade Downey、Jed L. Hubbs

  DOI：10.1021/ja035509j

  日期：2003.7.1

  enantioselective aldol reaction of N-propionylthiazolidinethione and representative aldehydes is disclosed. The reaction is catalyzed by [Ni(S,S)-t-BuBox](Otf)2. Enolization is effected by 2,6-lutidine, and TMSOTf facilitates catalyst turnover. Syn diastereoselectivities range from 88:12 to 97:3, and enantioselectivities are 90% or greater. Both aromatic and enolizable aliphatic aldehydes are included within

  公开了N-丙酰基噻唑烷硫酮和代表性醛的对映选择性羟醛反应。该反应由 [Ni(S,S)-t-BuBox](Otf)2 催化。烯醇化受 2,6-二甲基吡啶影响，TMSOTf 促进催化剂周转。合成非对映选择性范围为 88:12 至 97:3，对映选择性为 90% 或更高。芳香族和可烯醇化的脂肪族醛都包括在该醛醇加成过程的范围内。