(6R)-6-[[(tert-butyldimethylsilyl)oxy]methyl]tetrahydro-2-methylpyrrolo[1,2-a]pyrazine-1,4,8(8aH)-trione | 1096711-41-9

• 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: (6R)-6-[[(tert-butyldimethylsilyl)oxy]methyl]tetrahydro-2-methylpyrrolo[1,2-a]pyrazine-1,4,8(8aH)-trione
• 英文别名: (6R)-6-[[tert-butyl(diphenyl)silyl]oxymethyl]-2-methyl-3,6,7,8a-tetrahydropyrrolo[1,2-a]pyrazine-1,4,8-trione
• CAS: 1096711-41-9
• 化学式: C₂₅H₃₀N₂O₄Si
• 分子量: 450.61
• InChiKey: NDUVOUFYJITGOB-FKSKYRLFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.57
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  66.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (6R)-6-[[(tert-butyldimethylsilyl)oxy]methyl]tetrahydro-2-methylpyrrolo[1,2-a]pyrazine-1,4,8(8aH)-trione 在 2,6-二甲基吡啶 、 sodium tetrahydroborate 、 水 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.02h， 生成 (6R,8S,8aR)-8a-(([(tert-butyldimethylsilyl)oxy]methyl)sulfanyl)-6-([(tert-butyl-diphenylsilyl)oxy]methyl)-2-methyl-8-[(triethylsilyl)oxy]octahydropyrrolo[1,2-a]piperazine-1,4-dione
  参考文献：
  名称：

  Synthetic studies related to MPC1001: formation of a model epidithiodiketopiperazine

  摘要：

  A tricyclic epidithiodiketopiperazine was prepared having structural features related to the antitumor antibiotic MPC1001. The method is based on the use of the sulfenylating agent p-MeC6H4S(O-2)SCH2OSiMe2Bu-t to introduce two protected sulfur atoms in a sequential and stereocontrolled manner. Fluoride-induced deprotection to remove the CH2OSiMe2Bu-t units and release two sulfhydryl groups, followed by in situ oxidation, then generated the required bridged disulfide. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.01.055
• 作为产物：
  描述：

  phenyl [2-[(2R)-2-[[(tert-butyldiphenylsilyl)oxy]methyl]-4-oxopyrrolidin-1-yl]-2-oxoethyl]methylcarbamate 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 0.33h， 生成 (6R)-6-[[(tert-butyldimethylsilyl)oxy]methyl]tetrahydro-2-methylpyrrolo[1,2-a]pyrazine-1,4,8(8aH)-trione
  参考文献：
  名称：

  用于硫保护的[[（叔丁基）二甲基甲硅烷基]氧基]甲基

  摘要：

  芳族和脂族硫醇可以通过与保护吨-BuMe 2的SiOCH 2氯在DMF中，在碱（2,6-二甲基吡啶或质子海绵）的存在; 所得吨-BuMe 2的SiOCH 2 SR或吨-BuMe 2的SiOCH 2 SAR通过用布顺序处理脱保护4 NF和我2，得到对称的二硫化物。脱保护的另一种方式涉及与亚磺酰氯反应。该过程产生不对称的二硫键，并用Me（CH 2）11 SCH 2 OSiMe 2 Bu-t和三个亚磺酰氯。

  DOI：

  10.1021/ol2002573

文献信息

• [[(<i>tert</i>-Butyl)dimethylsilyl]oxy]methyl Group for Sulfur Protection
  作者：Lihong Wang、Derrick L. J. Clive

  DOI：10.1021/ol2002573

  日期：2011.4.1

  aliphatic thiols can be protected by reaction with t-BuMe2SiOCH2Cl in DMF in the presence of a base (2,6-lutidine or proton sponge); the resulting t-BuMe2SiOCH2SR or t-BuMe2SiOCH2SAr are deprotected by sequential treatment with Bu4NF and I2 to give symmetrical disulfides. Another mode of deprotection involves reaction with a sulfenyl chloride; this process gives an unsymmetrical disulfide and was examined

  芳族和脂族硫醇可以通过与保护吨-BuMe 2的SiOCH 2氯在DMF中，在碱（2,6-二甲基吡啶或质子海绵）的存在; 所得吨-BuMe 2的SiOCH 2 SR或吨-BuMe 2的SiOCH 2 SAR通过用布顺序处理脱保护4 NF和我2，得到对称的二硫化物。脱保护的另一种方式涉及与亚磺酰氯反应。该过程产生不对称的二硫键，并用Me（CH 2）11 SCH 2 OSiMe 2 Bu-t和三个亚磺酰氯。
• Asymmetric Synthesis of the ABC-Ring System of the Antitumor Antibiotic MPC1001
  作者：Jianbiao Peng、Derrick L. J. Clive

  DOI：10.1021/jo802344t

  日期：2009.1.16

  trans-4-Hydroxy-L-proline was converted into a tricyclic compound representing three contiguous rings of the anticancer antibiotic MPC1001. The tricyclic model contains the dihydrooxepin and diketopiperazine Subunits, as well as one of the Sulfur atoms of the natural product. The diketopiperazine unit was formed by a new method that involves cyclization of an enolate onto the carbonyl of a phenyl carbamate, and the dihydrooxepin ring was generated by using an acid-induced cyclization of an alcohol onto the beta-carbon of a vinylogous amide.
• Synthetic studies related to MPC1001: formation of a model epidithiodiketopiperazine
  作者：Lihong Wang、Derrick L.J. Clive

  DOI：10.1016/j.tetlet.2012.01.055

  日期：2012.3

  A tricyclic epidithiodiketopiperazine was prepared having structural features related to the antitumor antibiotic MPC1001. The method is based on the use of the sulfenylating agent p-MeC6H4S(O-2)SCH2OSiMe2Bu-t to introduce two protected sulfur atoms in a sequential and stereocontrolled manner. Fluoride-induced deprotection to remove the CH2OSiMe2Bu-t units and release two sulfhydryl groups, followed by in situ oxidation, then generated the required bridged disulfide. (C) 2012 Elsevier Ltd. All rights reserved.