(3R/S,2'S)-3-(N-(tert-butoxycarbonyl)pyrrolidin-2'yl)-1-(trimethylsilyl)prop-1-yn-3-ol | 918134-21-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (3R/S,2'S)-3-(N-(tert-butoxycarbonyl)pyrrolidin-2'yl)-1-(trimethylsilyl)prop-1-yn-3-ol
• 英文别名: (3R/S,2'S)-3-[N-(tert-butoxycarbonyl)pyrrolidin-2'yl]-1-(trimethylsilyl)prop-1-yn-3-ol；tert-butyl (2S)-2-(1-hydroxy-3-trimethylsilylprop-2-ynyl)pyrrolidine-1-carboxylate
• CAS: 918134-21-1
• 化学式: C₁₅H₂₇NO₃Si
• 分子量: 297.47
• InChiKey: QIRKFIBCINTPDK-UEWDXFNNSA-N

物化性质

• 沸点：
  374.3±12.0 °C(Predicted)
• 密度：
  1.043±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.63
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R/S,2'S)-3-(N-(tert-butoxycarbonyl)pyrrolidin-2'yl)-1-(trimethylsilyl)prop-1-yn-3-ol 在 盐酸 、 硫酸 、 potassium hydride 、 对甲苯磺酸 、 N,N'-羰基二咪唑 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙腈 为溶剂， 反应 46.0h， 生成 tert-butyl (2S,4'R,2'S)-2-isopropyl-4-(pyrrolidin-2'yl)-3-oxohex-5-ynoate
  参考文献：
  名称：

  Synthesis of proline-valine pseudodipeptide enol lactones, serine protease inhibitors

  摘要：

  Pseudodipeptides of proline-valine that incorporate protio or halo enol lactone moieties have been synthesized from common acetylenic acid precursors; in each case, two diasteromers were prepared in enantiomerically pure form. The preparation began with isomeric propargylic alcohols derived from L-prolinal, which are further elaborated into the methyleneoxy valine pseudodipeptide analogues via an oxalactam intermediate. Stereochemical assignments were made by comparisons of nuclear Overhauser enhancement factors. The pseudodipeptide acetylenic acids could by cyclized to the protio enol lactones by mercuric salts and could be elaborated to tetrapeptide analogues either before or after cyclization. The relative stability of the two diastereomeric enol lactone systems toward intramolecular acyl transfer could be rationalized by molecular mechanics energy calculations on ground-state and tetrahedral intermediates believed to be involved in the reaction. While the halo enol lactones derived from the pseudotetrapeptides proved to be very unstable, they could be prepared from the n-butyl carbamate derivatives of the dipeptide. An evaluation of these protio and halo enol lactone systems as inhibitors of serine proteases will be discussed elsewhere.

  DOI：

  10.1021/jo00008a011
• 作为产物：
  描述：

  (S)-N-Boc-吡咯烷-2-甲醛 N-(叔丁氧羰基)-L-脯氨醛 以91%的产率得到
  参考文献：
  名称：

  REED, PETER E.;KATZENELLENBOGEN, JOHN A., J. ORG. CHEM., 56,(1991) N, C. 2624-2634

  摘要：

  DOI：

文献信息

• Synthesis and Thermal Reactivity of Pyrrolidine- and 2-Pyrrolidinone-Fused Cyclic Enediynes
  作者：Amit Basak、Basab Roy

  DOI：10.1055/s-2006-950278

  日期：2006.10

  Various bicyclic enediynes containing pyrrolidine and pyrrolidinone moieties were synthesised. Thermal reactivity studies indicated the lowering of the onset temperature for Bergman cyclisation upon fusion of these heterocyclic systems onto the cyclic enediyne.

  合成了各种含有吡咯烷和吡咯烷酮部分的双环烯二炔。热反应性研究表明，在这些杂环系统融合到环烯二炔上时，伯格曼环化的起始温度降低。
• InCl3 catalyzed carbene insertion into O–H bonds: efficient synthesis of ethers
  作者：Palakodety Radha Krishna、Y. Lakshmi Prapurna、Munagala Alivelu

  DOI：10.1016/j.tetlet.2011.04.099

  日期：2011.7

  An efficient InCl3 mediated insertion of the carbene fragment (:CHCO2Et), generated in situ from ethyl diazoacetate into O-H bond of a series of saturated and unsaturated alcohols under mild conditions has been developed to afford the corresponding ethers as exclusive products in good to high yields (70-95%) and in shorter reaction times. In the case of unsaturated alcohols, the reaction proceeded with unprecedented selectivity resulting in ethers as the only products and in high yields. (C) 2011 Elsevier Ltd. All rights reserved.
• REED, PETER E.;KATZENELLENBOGEN, JOHN A., J. ORG. CHEM., 56,(1991) N, C. 2624-2634
  作者：REED, PETER E.、KATZENELLENBOGEN, JOHN A.

  DOI：——

  日期：——
• Synthesis of proline-valine pseudodipeptide enol lactones, serine protease inhibitors
  作者：Peter E. Reed、John A. Katzenellenbogen

  DOI：10.1021/jo00008a011

  日期：1991.4

  Pseudodipeptides of proline-valine that incorporate protio or halo enol lactone moieties have been synthesized from common acetylenic acid precursors; in each case, two diasteromers were prepared in enantiomerically pure form. The preparation began with isomeric propargylic alcohols derived from L-prolinal, which are further elaborated into the methyleneoxy valine pseudodipeptide analogues via an oxalactam intermediate. Stereochemical assignments were made by comparisons of nuclear Overhauser enhancement factors. The pseudodipeptide acetylenic acids could by cyclized to the protio enol lactones by mercuric salts and could be elaborated to tetrapeptide analogues either before or after cyclization. The relative stability of the two diastereomeric enol lactone systems toward intramolecular acyl transfer could be rationalized by molecular mechanics energy calculations on ground-state and tetrahedral intermediates believed to be involved in the reaction. While the halo enol lactones derived from the pseudotetrapeptides proved to be very unstable, they could be prepared from the n-butyl carbamate derivatives of the dipeptide. An evaluation of these protio and halo enol lactone systems as inhibitors of serine proteases will be discussed elsewhere.