(5R,1'R,2'S)-5-(1'-tert-butyldimethylsiloxy-2'-hydroxy)propyl-2-methylpyrazolidin-3-one | 244190-65-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (5R,1'R,2'S)-5-(1'-tert-butyldimethylsiloxy-2'-hydroxy)propyl-2-methylpyrazolidin-3-one
• 英文别名: (5R)-5-[(1R,2S)-1-[tert-butyl(dimethyl)silyl]oxy-2-hydroxypropyl]-2-methylpyrazolidin-3-one
• CAS: 244190-65-6
• 化学式: C₁₃H₂₈N₂O₃Si
• 分子量: 288.462
• InChiKey: DJEYLHMHDCVLAP-UMNHJUIQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.49
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  61.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (5R,1'R,2'S)-5-(1'-tert-butyldimethylsiloxy-2'-hydroxy)propyl-2-methylpyrazolidin-3-one 在 四丁基氟化铵 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 4.0h， 生成 (2R,4S,5R,6S)-1,9-diaza-2-butoxycarbonyl-5-hydroxy-4,9-dimethyl-3-oxa-8-oxobicyclo[4.3.0]nonane
  参考文献：
  名称：

  β-内酰胺类抗生素的吡唑烷酮类似物的合成

  摘要：

  5位取代的吡唑烷基-3-酮可容易地通过将肼与2,3-不饱和糖1,5-内酯进行共轭加成-重排而获得，与2 Ms当量反应。炔二羧酸二甲酯（DMAD）生成相应的2,3-二氢-5,6,7-三甲氧基羰基-5-甲氧基羰基甲基-1-氧代-1 H，5 H-吡唑并[1,2- a吡唑类。反应通过将吡唑烷丁-3-one的胺基加至DMAD，加合物的重排导致偶氮甲亚胺-亚胺内立基，接着是第二DMAD分子的1，3-偶极环加成而进行。所述环加成产物可以经历从多元醇侧链到双键的分子内羟基加成以产生三环化合物。吡唑烷丁-3-酮与DMAD的反应伴随着几种副产物的形成，对其的鉴定使得可能提出反应途径。

  DOI：

  10.1016/s0040-4020(01)01195-4
• 作为产物：
  描述：

  甲基肼 、 (2S,3R)-3-[tert-butyl(dimethyl)silyl]oxy-2-methyl-2,3-dihydropyran-6-one 以 甲醇 为溶剂， 以34%的产率得到(5R,1'R,2'S)-5-(1'-tert-butyldimethylsiloxy-2'-hydroxy)propyl-2-methylpyrazolidin-3-one
  参考文献：
  名称：

  Configurational Assignment of 5-Substituted Pyrazolidin-3-ones Using Circular Dichroism Spectroscopy

  摘要：

  The chiroptical properties of the title compounds bearing various substituents at the N(1) and N(2) nitrogen atoms are discussed. It was found that the sign of the n-pi* Cotton effect centered at about the 230-250 nm region can be correlated with the absolute configuration of the stereogenic center at C(5). It was also found that the sign of this Cotton effect is predictable by Weigang's lactam sector rule. MNIX calculations, supported by X-ray measurements, showed that substituents at the nitrogen atoms significantly affect the conformation of the five-membered ring. It was additionally concluded that the conformation of the five-membered ring in 5-substituted pyrazolidin-3-ones is the sign-determining factor for an n-pi* transition.

  DOI：

  10.1021/jo9803232

文献信息

• Configurational Assignment of 5-Substituted Pyrazolidin-3-ones Using Circular Dichroism Spectroscopy
  作者：Jadwiga Frelek、Irma Panfil、Zofia Urbańczyk-Lipkowska、Marek Chmielewski

  DOI：10.1021/jo9803232

  日期：1999.8.1

  The chiroptical properties of the title compounds bearing various substituents at the N(1) and N(2) nitrogen atoms are discussed. It was found that the sign of the n-pi* Cotton effect centered at about the 230-250 nm region can be correlated with the absolute configuration of the stereogenic center at C(5). It was also found that the sign of this Cotton effect is predictable by Weigang's lactam sector rule. MNIX calculations, supported by X-ray measurements, showed that substituents at the nitrogen atoms significantly affect the conformation of the five-membered ring. It was additionally concluded that the conformation of the five-membered ring in 5-substituted pyrazolidin-3-ones is the sign-determining factor for an n-pi* transition.
• Synthesis of pyrazolidinone analogs of β-lactam antibiotics
  作者：Irma Panfil、Zofia Urbańczyk-Lipkowska、Kinga Suwińska、Jolanta Solecka、Marek Chmielewski

  DOI：10.1016/s0040-4020(01)01195-4

  日期：2002.2

  easily available by the conjugate addition–rearrangement of hydrazine to the 2,3-unsaturated sugar 1,5-lactones, react with 2 Ms equiv. of dimethyl acetylenedicarboxylate (DMAD) to give corresponding 2,3-dihydro-5,6,7-trimethoxycarbonyl-5-methoxycarbonylmethyl-1-oxo-1H,5H-pyrazolo[1,2-a]pyrazoles. Reaction proceeds via addition of the amine group of pyrazolidin-3-one to DMAD, rearrangement of the adduct

  5位取代的吡唑烷基-3-酮可容易地通过将肼与2,3-不饱和糖1,5-内酯进行共轭加成-重排而获得，与2 Ms当量反应。炔二羧酸二甲酯（DMAD）生成相应的2,3-二氢-5,6,7-三甲氧基羰基-5-甲氧基羰基甲基-1-氧代-1 H，5 H-吡唑并[1,2- a吡唑类。反应通过将吡唑烷丁-3-one的胺基加至DMAD，加合物的重排导致偶氮甲亚胺-亚胺内立基，接着是第二DMAD分子的1，3-偶极环加成而进行。所述环加成产物可以经历从多元醇侧链到双键的分子内羟基加成以产生三环化合物。吡唑烷丁-3-酮与DMAD的反应伴随着几种副产物的形成，对其的鉴定使得可能提出反应途径。