(E)-ethyl 6-{[(1,1-dimethyl)ethyl dimethylsilyl]oxy}-5-(S)-[(N-imidazole-thiocarbonyl)oxy]-2-hexenoate | 501373-18-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (E)-ethyl 6-{[(1,1-dimethyl)ethyl dimethylsilyl]oxy}-5-(S)-[(N-imidazole-thiocarbonyl)oxy]-2-hexenoate
• 英文别名: ethyl (E,5S)-6-[tert-butyl(dimethyl)silyl]oxy-5-(imidazole-1-carbothioyloxy)hex-2-enoate
• CAS: 501373-18-8
• 化学式: C₁₈H₃₀N₂O₄SSi
• 分子量: 398.599
• InChiKey: KKCRXMBEFSBHMB-HQPKTYMTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.93
• 重原子数：
  26
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  94.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (E)-ethyl 6-{[(1,1-dimethyl)ethyl dimethylsilyl]oxy}-5-(S)-[(N-imidazole-thiocarbonyl)oxy]-2-hexenoate 在 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 以58%的产率得到trans-[5-(tert-butyl-dimethyl-silanyloxymethyl)-2-thioxo-tetrahydro-furan-3-yl]-acetic acid ethyl aster
  参考文献：
  名称：

  A New Reaction Manifold for the Barton Radical Intermediates:  Synthesis of N-Heterocyclic Furanosides and Pyranosides via the Formation of the C₁−C₂ Bond

  摘要：

  The first radical intermediate in the thiourethane-mediated deoxygenation of an alcohol (Barton-McCombie reaction) can participate in an exo-hex-5-enyl- or exo-hept-6-enyl-type radical cyclization when a suitable radical acceptor (e.g., alpha,beta-unsaturated ester, oxime ether, or hydrazone) is appropriately placed. Carbohydrate-derived imidazolyl and triazolyl thiourethanes with such acceptors, upon addition to excess of a good hydride donor (reverse addition), undergo efficient cyclization reactions to give N-heterocyclic furanosides, and, surprisingly even N-pyranosides. Depending on the acceptor, glycosides with either a C(2)()-amino or a C(2)()-carbon substituent are formed.

  DOI：

  10.1021/ja028617z
• 作为产物：
  描述：

  2-Hexenoic acid, 5-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-6-hydroxy-,ethyl ester, (2E,5S)- 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 54.0h， 生成 (E)-ethyl 6-{[(1,1-dimethyl)ethyl dimethylsilyl]oxy}-5-(S)-[(N-imidazole-thiocarbonyl)oxy]-2-hexenoate
  参考文献：
  名称：

  A New Reaction Manifold for the Barton Radical Intermediates:  Synthesis of N-Heterocyclic Furanosides and Pyranosides via the Formation of the C₁−C₂ Bond

  摘要：

  The first radical intermediate in the thiourethane-mediated deoxygenation of an alcohol (Barton-McCombie reaction) can participate in an exo-hex-5-enyl- or exo-hept-6-enyl-type radical cyclization when a suitable radical acceptor (e.g., alpha,beta-unsaturated ester, oxime ether, or hydrazone) is appropriately placed. Carbohydrate-derived imidazolyl and triazolyl thiourethanes with such acceptors, upon addition to excess of a good hydride donor (reverse addition), undergo efficient cyclization reactions to give N-heterocyclic furanosides, and, surprisingly even N-pyranosides. Depending on the acceptor, glycosides with either a C(2)()-amino or a C(2)()-carbon substituent are formed.

  DOI：

  10.1021/ja028617z

文献信息

• A New Reaction Manifold for the Barton Radical Intermediates:  Synthesis of <i>N</i>-Heterocyclic Furanosides and Pyranosides via the Formation of the C₁−C₂ Bond
  作者：Jong Uk Rhee、Brian I. Bliss、T. V. RajanBabu

  DOI：10.1021/ja028617z

  日期：2003.2.1

  The first radical intermediate in the thiourethane-mediated deoxygenation of an alcohol (Barton-McCombie reaction) can participate in an exo-hex-5-enyl- or exo-hept-6-enyl-type radical cyclization when a suitable radical acceptor (e.g., alpha,beta-unsaturated ester, oxime ether, or hydrazone) is appropriately placed. Carbohydrate-derived imidazolyl and triazolyl thiourethanes with such acceptors, upon addition to excess of a good hydride donor (reverse addition), undergo efficient cyclization reactions to give N-heterocyclic furanosides, and, surprisingly even N-pyranosides. Depending on the acceptor, glycosides with either a C(2)()-amino or a C(2)()-carbon substituent are formed.