(2S,3S,4E)-1-[(4-methylphenyl)sulfonyl]-4-[1-(benzyldimethylsilyl)ethylidene]-2-methoxycarbonyl-3-pyrrolidineacetaldehyde | 1259286-19-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (2S,3S,4E)-1-[(4-methylphenyl)sulfonyl]-4-[1-(benzyldimethylsilyl)ethylidene]-2-methoxycarbonyl-3-pyrrolidineacetaldehyde
• 英文别名: methyl (2S,3S,4E)-4-[1-[benzyl(dimethyl)silyl]ethylidene]-1-(4-methylphenyl)sulfonyl-3-(2-oxoethyl)pyrrolidine-2-carboxylate
• CAS: 1259286-19-5
• 化学式: C₂₆H₃₃NO₅SSi
• 分子量: 499.703
• InChiKey: WTUOXAIOJVAEIF-MMQUIWPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.09
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  89.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2S,3S,4E)-1-[(4-methylphenyl)sulfonyl]-4-[1-(benzyldimethylsilyl)ethylidene]-2-methoxycarbonyl-3-pyrrolidineacetaldehyde 在 sodium chlorite 、 sodium dihydrogenphosphate dihydrate 、 2-甲基-2-丁烯 作用下， 以 水 、 叔丁醇 为溶剂， 反应 0.5h， 生成 2-((2S,3S,E)-4-(1-(benzyldimethylsilyl)ethylidene)-2-(methoxycarbonyl)-1-tosylpyrrolidin-3-yl)acetic acid
  参考文献：
  名称：

  Stereocontrolled Total Syntheses of Isodomoic Acids G and H via a Unified Strategy

  摘要：

  Marine neuroexcitatory compounds isodomoic acids G and H were efficiently synthesized from a common intermediate using a silicon-based cross-coupling reaction. Dividing each target compound into the core fragment and the side-chain fragment enabled the synthesis to be convergent. The trans-2,3-disubstituted pyrrolidine core fragment was accessed through a diastereoselective rhodium-catalyzed carbonylative silylcarbocyclization reaction of a vinylglycine-derived 1,6-enyne. A stereochemically divergent desilylative iodination reaction was developed to convert the cyclization product to both E- and Z-alkenyl iodides, which would eventually lead to isodomoic acid G and isodomoic acid H, respectively. The late-stage alkenyl alkenyl silicon-based cross-coupling reaction uniting the core alkenyl iodides and the side-chain alkenylsilanol was achieved under mild conditions. Finally, two mild deprotections afforded the target molecules.

  DOI：

  10.1021/jo101790z
• 作为产物：
  描述：

  (S)-4-甲基-N-(2-氧代四氢呋喃-3-基)苯磺酰胺 在 (acetylacetonato)dicarbonylrhodium (l) 、 sodium tetrahydroborate 、 氯化亚砜 、 双氧水 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， -1.0~120.0 ℃ 、4.14 MPa 条件下， 反应 76.5h， 生成 、 (2S,3S,4E)-1-[(4-methylphenyl)sulfonyl]-4-[1-(benzyldimethylsilyl)ethylidene]-2-methoxycarbonyl-3-pyrrolidineacetaldehyde
  参考文献：
  名称：

  Stereocontrolled Total Syntheses of Isodomoic Acids G and H via a Unified Strategy

  摘要：

  Marine neuroexcitatory compounds isodomoic acids G and H were efficiently synthesized from a common intermediate using a silicon-based cross-coupling reaction. Dividing each target compound into the core fragment and the side-chain fragment enabled the synthesis to be convergent. The trans-2,3-disubstituted pyrrolidine core fragment was accessed through a diastereoselective rhodium-catalyzed carbonylative silylcarbocyclization reaction of a vinylglycine-derived 1,6-enyne. A stereochemically divergent desilylative iodination reaction was developed to convert the cyclization product to both E- and Z-alkenyl iodides, which would eventually lead to isodomoic acid G and isodomoic acid H, respectively. The late-stage alkenyl alkenyl silicon-based cross-coupling reaction uniting the core alkenyl iodides and the side-chain alkenylsilanol was achieved under mild conditions. Finally, two mild deprotections afforded the target molecules.

  DOI：

  10.1021/jo101790z