methyl (2S,3S,4E)-1-[(4-methylphenyl)sulfonyl]-4-[1-(benzyldimethylsilyl)ethylidene]-2-methoxycarbonyl-3-pyrrolidineacetate | 1259286-22-0

• 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: methyl (2S,3S,4E)-1-[(4-methylphenyl)sulfonyl]-4-[1-(benzyldimethylsilyl)ethylidene]-2-methoxycarbonyl-3-pyrrolidineacetate
• 英文别名: methyl (2S,3S,4E)-4-[1-[benzyl(dimethyl)silyl]ethylidene]-3-(2-methoxy-2-oxoethyl)-1-(4-methylphenyl)sulfonylpyrrolidine-2-carboxylate
• CAS: 1259286-22-0
• 化学式: C₂₇H₃₅NO₆SSi
• 分子量: 529.73
• InChiKey: HBPSPCOHBPUQDY-QUQMMJAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.07
• 重原子数：
  36
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  98.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl (2S,3S,4E)-1-[(4-methylphenyl)sulfonyl]-4-[1-(benzyldimethylsilyl)ethylidene]-2-methoxycarbonyl-3-pyrrolidineacetate 在 四丁基氟化铵 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 0.03h， 生成 methyl (2S,3S,4E)-1-[(4-methylphenyl)sulfonyl]-4-[1-(hydroxydimethylsilyl)ethylidene]-2-methoxycarbonyl-3-pyrrolidineacetate
  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：

  methyl (S)-4-iodo-2-((4-methylphenyl)sulfonamido)butanoate 在 (acetylacetonato)dicarbonylrhodium (l) 、 sodium chlorite 、 sodium tetrahydroborate 、 sodium dihydrogenphosphate dihydrate 、 2-甲基-2-丁烯 、 双氧水 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 、 水 、 甲苯 、 叔丁醇 为溶剂， -1.0~70.0 ℃ 、4.83 MPa 条件下， 反应 29.0h， 生成 methyl (2S,3S,4E)-1-[(4-methylphenyl)sulfonyl]-4-[1-(benzyldimethylsilyl)ethylidene]-2-methoxycarbonyl-3-pyrrolidineacetate
  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

文献信息

• Stereocontrolled Total Syntheses of Isodomoic Acids G and H via a Unified Strategy
  作者：Scott E. Denmark、Jack Hung-Chang Liu、Joseck M. Muhuhi

  DOI：10.1021/jo101790z

  日期：2011.1.7

  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.