N-(1,3-dipivaloyloxyprop-2-yl)-N-(pivaloyloxymethyl)acetamide

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-(1,3-dipivaloyloxyprop-2-yl)-N-(pivaloyloxymethyl)acetamide
• 英文别名: [2-[Acetyl(2,2-dimethylpropanoyloxymethyl)amino]-3-(2,2-dimethylpropanoyloxy)propyl] 2,2-dimethylpropanoate；[2-[acetyl(2,2-dimethylpropanoyloxymethyl)amino]-3-(2,2-dimethylpropanoyloxy)propyl] 2,2-dimethylpropanoate
• 化学式: C₂₁H₃₇NO₇
• 分子量: 415.527
• InChiKey: VGUJPZOVUJYNFZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  29
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  99.2
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  N-(1,3-dipivaloyloxyprop-2-yl)-N-(pivaloyloxymethyl)acetamide 、 胸腺嘧啶 在 N,O-双三甲硅基乙酰胺 、 三氟甲磺酸三甲基硅酯 作用下， 以 乙腈 为溶剂， 反应 49.0h， 以81%的产率得到1-[N-(1,3-dipivaloyloxyprop-2-yl)acetylaminomethyl]-5-methyl-1H,3H-pyrimidin-2,4-dione
  参考文献：
  名称：

  Studies on the Synthesis ofN′-Acetyl AZA-Analogues ofGanciclovir—Unexpected Liability ofN′-(2-Hydroxyethyl)-Azanucleosides Under Basic Conditions

  摘要：

  The O'-pivaloyl diesters of N'-acetyl-azanucleosides were obtained from N-[1,3-di(pivaloyloxy)prop-2-yl]-N-(pivaloyloxymethyl)acetamide and a silylated nucleobase under Vorbruggen's conditions. Unexpectedly, de-pivaloylation of the diesters under basic conditions afforded the corresponding nucleobase and N-acetylserinol. Mechanistic investigations showed that these products result from the following cascade of spontaneous transformations initiated by the mono de-pivaloylation of the starting diesters. N'-Deacetylation of the resultant mono-esters via the intramolecular N-O acetyl migration is the key step of the cascade; the corresponding NH-azanucleosides in the form of O-acetyl-O'-pivaloyl diesters are formed. Fragmentation of these diester intermediates gives the nucleobase and O-acetyl-O'-pivaloylserinol. Conversion of the latter to N-acetylserinol involves the selective O-N acetyl migration followed by de-pivaloylation of the resulting N-acetyl-O-pivaloylserinol.

  DOI：

  10.1080/15257770.2010.519367
• 作为产物：
  描述：

  O,O'-dipivaloylserinol hydrochloride 在 吡啶 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 121.0h， 生成 N-(1,3-dipivaloyloxyprop-2-yl)-N-(pivaloyloxymethyl)acetamide
  参考文献：
  名称：

  Studies on the Synthesis ofN′-Acetyl AZA-Analogues ofGanciclovir—Unexpected Liability ofN′-(2-Hydroxyethyl)-Azanucleosides Under Basic Conditions

  摘要：

  The O'-pivaloyl diesters of N'-acetyl-azanucleosides were obtained from N-[1,3-di(pivaloyloxy)prop-2-yl]-N-(pivaloyloxymethyl)acetamide and a silylated nucleobase under Vorbruggen's conditions. Unexpectedly, de-pivaloylation of the diesters under basic conditions afforded the corresponding nucleobase and N-acetylserinol. Mechanistic investigations showed that these products result from the following cascade of spontaneous transformations initiated by the mono de-pivaloylation of the starting diesters. N'-Deacetylation of the resultant mono-esters via the intramolecular N-O acetyl migration is the key step of the cascade; the corresponding NH-azanucleosides in the form of O-acetyl-O'-pivaloyl diesters are formed. Fragmentation of these diester intermediates gives the nucleobase and O-acetyl-O'-pivaloylserinol. Conversion of the latter to N-acetylserinol involves the selective O-N acetyl migration followed by de-pivaloylation of the resulting N-acetyl-O-pivaloylserinol.

  DOI：

  10.1080/15257770.2010.519367

文献信息

• Studies on the Synthesis of<i>N</i>′-Acetyl AZA-Analogues of<i>Ganciclovir</i>—Unexpected Liability of<i>N</i>′-(2-Hydroxyethyl)-Azanucleosides Under Basic Conditions
  作者：Mariola Koszytkowska-Stawińska

  DOI：10.1080/15257770.2010.519367

  日期：2010.10.6

  The O'-pivaloyl diesters of N'-acetyl-azanucleosides were obtained from N-[1,3-di(pivaloyloxy)prop-2-yl]-N-(pivaloyloxymethyl)acetamide and a silylated nucleobase under Vorbruggen's conditions. Unexpectedly, de-pivaloylation of the diesters under basic conditions afforded the corresponding nucleobase and N-acetylserinol. Mechanistic investigations showed that these products result from the following cascade of spontaneous transformations initiated by the mono de-pivaloylation of the starting diesters. N'-Deacetylation of the resultant mono-esters via the intramolecular N-O acetyl migration is the key step of the cascade; the corresponding NH-azanucleosides in the form of O-acetyl-O'-pivaloyl diesters are formed. Fragmentation of these diester intermediates gives the nucleobase and O-acetyl-O'-pivaloylserinol. Conversion of the latter to N-acetylserinol involves the selective O-N acetyl migration followed by de-pivaloylation of the resulting N-acetyl-O-pivaloylserinol.