(2SR,3SR,4SR)-Methyl N-(benzyloxycarbonyl)-2-(ethoxycarbonyl)-4-isopropenylpyrrolidine-3-acetate

• 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: (2SR,3SR,4SR)-Methyl N-(benzyloxycarbonyl)-2-(ethoxycarbonyl)-4-isopropenylpyrrolidine-3-acetate
• 英文别名: 1-O-benzyl 2-O-ethyl (2S,3S,4S)-3-(2-methoxy-2-oxoethyl)-4-prop-1-en-2-ylpyrrolidine-1,2-dicarboxylate
• 化学式: C₂₁H₂₇NO₆
• 分子量: 389.448
• InChiKey: CUAHJAXMEKOEAQ-SCTDSRPQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  82.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2SR,3SR,4SR)-Methyl N-(benzyloxycarbonyl)-2-(ethoxycarbonyl)-4-isopropenylpyrrolidine-3-acetate 在 sodium hydroxide 作用下， 反应 96.0h， 以97%的产率得到(+/-)-α-kainic acid
  参考文献：
  名称：

  A Concise, Stereocontrolled Thiazolium Ylide Approach to Kainic Acid

  摘要：

  Racemic alpha-kainic acid (1) has been prepared from (1SR,2SR,5RS)-ethyl (N-(benzyloxycarbonyl)3-aza-6-oxobicyclo[3.3.0] octane-2-carboxylate (11) in ca. 16% overall yield via a concise six-step synthetic sequence. Compound 11 is prepared pn a large scale in 50% yield via the [3 + 2] cycloaddition of thiazolium ylide 9 and 2-cyclopentenone, which provides the requisite 2,3-trans, 3,4-cis stereochemical array about the trisubstituted pyrrolidine nucleus in 1. Chemoselective addition of the one-to-one adduct of MeLi and TiCl4 to the ketone functionality in 11 followed by dehydration, oxidative ring opening, and nonbasic methylenation of the stereochemically labile C4 acetate moiety with CH2I2-Zn-TiCl4 affords the fully protected penultimate intermediate 17 which is exhaustively hydrolyzed to provide 1. This represents a highly efficient and stereocontrolled preparation of (+/-)-alpha-kainic acid.

  DOI：

  10.1021/jo00089a022
• 作为产物：
  描述：

  (1SR,2SR,5RS,6RS)-Ethyl N-(benzyloxycarbonyl)-3-aza-6-hydroxy-6-methylbicyclo[3.3.0]octane-2-carboxylate 在 ruthenium(IV) oxide 、 sodium periodate 、 三氟化硼乙醚 、 四氯化钛 、 potassium carbonate 、 锌 作用下， 以 四氢呋喃 、 四氯化碳 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 39.0h， 生成 (2SR,3SR,4SR)-Methyl N-(benzyloxycarbonyl)-2-(ethoxycarbonyl)-4-isopropenylpyrrolidine-3-acetate
  参考文献：
  名称：

  A Concise, Stereocontrolled Thiazolium Ylide Approach to Kainic Acid

  摘要：

  Racemic alpha-kainic acid (1) has been prepared from (1SR,2SR,5RS)-ethyl (N-(benzyloxycarbonyl)3-aza-6-oxobicyclo[3.3.0] octane-2-carboxylate (11) in ca. 16% overall yield via a concise six-step synthetic sequence. Compound 11 is prepared pn a large scale in 50% yield via the [3 + 2] cycloaddition of thiazolium ylide 9 and 2-cyclopentenone, which provides the requisite 2,3-trans, 3,4-cis stereochemical array about the trisubstituted pyrrolidine nucleus in 1. Chemoselective addition of the one-to-one adduct of MeLi and TiCl4 to the ketone functionality in 11 followed by dehydration, oxidative ring opening, and nonbasic methylenation of the stereochemically labile C4 acetate moiety with CH2I2-Zn-TiCl4 affords the fully protected penultimate intermediate 17 which is exhaustively hydrolyzed to provide 1. This represents a highly efficient and stereocontrolled preparation of (+/-)-alpha-kainic acid.

  DOI：

  10.1021/jo00089a022

文献信息

• A Concise, Stereocontrolled Thiazolium Ylide Approach to Kainic Acid
  作者：James A. Monn、Matthew J. Valli

  DOI：10.1021/jo00089a022

  日期：1994.5

  Racemic alpha-kainic acid (1) has been prepared from (1SR,2SR,5RS)-ethyl (N-(benzyloxycarbonyl)3-aza-6-oxobicyclo[3.3.0] octane-2-carboxylate (11) in ca. 16% overall yield via a concise six-step synthetic sequence. Compound 11 is prepared pn a large scale in 50% yield via the [3 + 2] cycloaddition of thiazolium ylide 9 and 2-cyclopentenone, which provides the requisite 2,3-trans, 3,4-cis stereochemical array about the trisubstituted pyrrolidine nucleus in 1. Chemoselective addition of the one-to-one adduct of MeLi and TiCl4 to the ketone functionality in 11 followed by dehydration, oxidative ring opening, and nonbasic methylenation of the stereochemically labile C4 acetate moiety with CH2I2-Zn-TiCl4 affords the fully protected penultimate intermediate 17 which is exhaustively hydrolyzed to provide 1. This represents a highly efficient and stereocontrolled preparation of (+/-)-alpha-kainic acid.