tert-butyl (2S,4R,2'S)-4-(N-(n-butyloxycarbonyl)pyrrolidin-2'yl)-2-isopropyl-3-oxahex-5-ynoate | 132127-57-2

• 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: tert-butyl (2S,4R,2'S)-4-(N-(n-butyloxycarbonyl)pyrrolidin-2'yl)-2-isopropyl-3-oxahex-5-ynoate
• 英文别名: tert-butyl (2S,4R,2'S)-4-[N-(n-butyloxycarbonyl)pyrrolidin-2'yl]-2-isopropyl-3-oxahex-5-ynoate；butyl (2S)-2-[(1R)-1-[(2S)-3-methyl-1-[(2-methylpropan-2-yl)oxy]-1-oxobutan-2-yl]oxyprop-2-ynyl]pyrrolidine-1-carboxylate
• CAS: 132127-57-2
• 化学式: C₂₁H₃₅NO₅
• 分子量: 381.513
• InChiKey: IWRLBYBHSOYKJV-KSZLIROESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.77
• 重原子数：
  27.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  65.07
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  tert-butyl (2S,4R,2'S)-4-(N-(n-butyloxycarbonyl)pyrrolidin-2'yl)-2-isopropyl-3-oxahex-5-ynoate 在 N-溴代丁二酰亚胺(NBS) 、 potassium hydrogencarbonate 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 53.5h， 生成 (3S,5S,2'S)-5-(N-(n-butoxycarbonyl)pyrrolidin-2'-yl)-6(E)-(bromomethylene)-3-isopropyl-4-oxatetrahydro-2-pyranone
  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：

  N-Boc-L-脯氨醇 在 N-甲基吗啉 、 盐酸 、 草酰氯 、 硫酸 、 乙基溴化镁 、 potassium hydride 、 对甲苯磺酸 、 二甲基亚砜 、 N,N-二异丙基乙胺 、 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 50.33h， 生成 tert-butyl (2S,4R,2'S)-4-(N-(n-butyloxycarbonyl)pyrrolidin-2'yl)-2-isopropyl-3-oxahex-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

文献信息

• 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.