<2S-<2R*<(R*),α(S*),β(S*)>>>-1-<(1,1-Dimethylethoxy)carbonyl>-β-methoxy-α-methyl-2-pyrrolidinepropanoic acid 2-hydroxy-1,2,2-triphenylethyl ester | 133164-07-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: <2S-<2R*<(R*),α(S*),β(S*)>>>-1-<(1,1-Dimethylethoxy)carbonyl>-β-methoxy-α-methyl-2-pyrrolidinepropanoic acid 2-hydroxy-1,2,2-triphenylethyl ester
• 英文别名: tert-butyl (2S)-2-[(1R,2R)-3-[(1S)-2-hydroxy-1,2,2-triphenylethoxy]-1-methoxy-2-methyl-3-oxopropyl]pyrrolidine-1-carboxylate
• CAS: 133164-07-5
• 化学式: C₃₄H₄₁NO₆
• 分子量: 559.703
• InChiKey: RZVCQRZNBMAJPO-AYYXBPQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  41
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  85.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  <2S-<2R*<(R*),α(S*),β(S*)>>>-1-<(1,1-Dimethylethoxy)carbonyl>-β-methoxy-α-methyl-2-pyrrolidinepropanoic acid 2-hydroxy-1,2,2-triphenylethyl ester 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 反应 12.0h， 以94%的产率得到((2R,3R)-3-((S)-1-(tert丁氧基羰基)吡咯烷-2-基)-3-甲氧基-2-甲基丙酸
  参考文献：
  名称：

  The Dolastatins. 17. Synthesis of Dolaproine and Related Diastereoisomers

  摘要：

  A special challenge in accomplishing the total synthesis of dolastatin 10(1) entailed deducing the absolute configuration of the new beta-methoxy-gamma-amino acid component dolaproine (2) as 2S,2'R,3'R and devising a stereoselective synthesis. Synthesis of this unusual (S)-proline-derived unit as its N-tert-butoxycarbonyl derivative (9b) and three stereoisomers (9a, 9c, 9d) has been summarized. The diastereoisomers were assembled by an aldol condensation between aldehyde 5, derived from (S)-proline, with chiral propionate 6, followed by methylation and cleavage of the chiral directing ester group by hydrogenolysis to afford methyl ethers 9a-d. The absolute stereochemistry of the diastereoisomers was determined by a combination of X-ray crystallographic analyses (of 9a and lactam 11b formed from isomer 7a) and high-field (400 MHz) NMR studies. By using each of these isomers in a series of dolastatin 10 syntheses the stereochemistry of the dolaproine (2) unit of natural (-)-dolastatin 10 (1) was shown to be 2S,2'R,3'R.

  DOI：

  10.1021/jo00100a034
• 作为产物：
  描述：

  L-扁桃酸甲酯 在 吡啶 、 正丁基锂 、 三氟化硼乙醚 、 potassium tert-butylate 、 二异丙胺 、 magnesium bromide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 32.08h， 生成 <2S-<2R*<(R*),α(S*),β(S*)>>>-1-<(1,1-Dimethylethoxy)carbonyl>-β-methoxy-α-methyl-2-pyrrolidinepropanoic acid 2-hydroxy-1,2,2-triphenylethyl ester
  参考文献：
  名称：

  The Dolastatins. 17. Synthesis of Dolaproine and Related Diastereoisomers

  摘要：

  A special challenge in accomplishing the total synthesis of dolastatin 10(1) entailed deducing the absolute configuration of the new beta-methoxy-gamma-amino acid component dolaproine (2) as 2S,2'R,3'R and devising a stereoselective synthesis. Synthesis of this unusual (S)-proline-derived unit as its N-tert-butoxycarbonyl derivative (9b) and three stereoisomers (9a, 9c, 9d) has been summarized. The diastereoisomers were assembled by an aldol condensation between aldehyde 5, derived from (S)-proline, with chiral propionate 6, followed by methylation and cleavage of the chiral directing ester group by hydrogenolysis to afford methyl ethers 9a-d. The absolute stereochemistry of the diastereoisomers was determined by a combination of X-ray crystallographic analyses (of 9a and lactam 11b formed from isomer 7a) and high-field (400 MHz) NMR studies. By using each of these isomers in a series of dolastatin 10 syntheses the stereochemistry of the dolaproine (2) unit of natural (-)-dolastatin 10 (1) was shown to be 2S,2'R,3'R.

  DOI：

  10.1021/jo00100a034