(S)-2-(Propionyloxy)-1,1,2-triphenylethanol | 133120-82-8

• 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: (S)-2-(Propionyloxy)-1,1,2-triphenylethanol
• 英文别名: 2S-Propionyloxy-1,1,2-triphenylethanol；[(1S)-2-hydroxy-1,2,2-triphenylethyl] propanoate
• CAS: 133120-82-8
• 化学式: C₂₃H₂₂O₃
• 分子量: 346.426
• InChiKey: OBFBJPKHBZESIY-QFIPXVFZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-2-(Propionyloxy)-1,1,2-triphenylethanol 在 正丁基锂 、 Proton Sponge 、 二异丙胺 、 magnesium bromide 作用下， 以 二氯甲烷 为溶剂， 反应 41.5h， 生成 <2S-<2R*<(R*),α(R*),β(R*)>>>-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
• 作为产物：
  描述：

  L-扁桃酸甲酯 在 吡啶 作用下， 以 乙醚 为溶剂， 反应 25.5h， 生成 (S)-2-(Propionyloxy)-1,1,2-triphenylethanol
  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

文献信息

• US4978744A
  申请人：——

  公开号：US4978744A

  公开（公告）日：1990-12-18
• The Dolastatins. 17. Synthesis of Dolaproine and Related Diastereoisomers
  作者：George R. Pettit、Sheo Bux Singh、Delbert L. Herald、Paul Lloyd-Williams、Darko Kantoci、Douglas D. Burkett、Jozsef Barkoczy、Fiona Hogan、Terah R. Wardlaw

  DOI：10.1021/jo00100a034

  日期：1994.10

  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.