4-tert-Butoxymethyl-4-methyl-5-methylene-pyrrolidin-2-one | 197068-20-5

• 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: 4-tert-Butoxymethyl-4-methyl-5-methylene-pyrrolidin-2-one
• 英文别名: 4-Methyl-5-methylidene-4-[(2-methylpropan-2-yl)oxymethyl]pyrrolidin-2-one
• CAS: 197068-20-5
• 化学式: C₁₁H₁₉NO₂
• 分子量: 197.277
• InChiKey: ZNDCWQLDTBTTEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-tert-Butoxymethyl-4-methyl-5-methylene-pyrrolidin-2-one 在 N-碘代丁二酰亚胺 、 potassium tert-butylate 、 亚磷酸三乙酯 作用下， 以 xylene 、 叔丁醇 、 苯 为溶剂， 生成 5-[(S)-4-((2S,3R,5R,6R)-3,5-Bis-benzyloxy-6-methyl-tetrahydro-pyran-2-yl)-5-[1-iodo-meth-(Z)-ylidene]-4-methyl-pyrrolidin-(2Z)-ylidenemethyl]-4-tert-butoxymethyl-4-methyl-3,4-dihydro-pyrrol-2-one
  参考文献：
  名称：

  Total Synthesis of the Proposed Structure of (+)-Tolyporphin AO,O-Diacetate

  摘要：

  Four monocyclic precursors were assembled in the total synthesis of the proposed structure 1-A of (+)-tolyporphin A O,O-diacetate (X=Ac). Comparison of the spectroscopic data demonstrated that synthetic tolyporphin O,O-diacetate did not match the O,O-diacetate prepared from natural (+)-tolyporphin A (X=H), calling for a structural revision of this class of natural products. On the basis of a series of NMR experiments including synthetic intermediates, the structure of tolyporphin A is concluded to be 1-B, in which the configurations of quaternary centers C7 and C17 are opposite to those in the originally proposed structure.

  DOI：

  10.1002/(sici)1521-3773(19990401)38:7<923::aid-anie923>3.0.co;2-7
• 作为产物：
  描述：

  α-甲基-γ-丁内酯 在 硫酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 16.0h， 生成 4-tert-Butoxymethyl-4-methyl-5-methylene-pyrrolidin-2-one
  参考文献：
  名称：

  Extension of the Eschenmoser sulfide contraction/iminoester cyclization method to the synthesis of tolyporphin chromophore

  摘要：

  Tolyporphin chromophore 2 has been synthesized by performing a double-retroaldol/oxidation sequence on an octahydroporphyrin precursor 28 prepared by using the Eschenmoser sulfide-contraction/iminoester-condensation method. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01601-8

文献信息

• Synthesis and Structure of Tolyporphin A <i>O,O</i>-Diacetate
  作者：Wengui Wang、Yoshito Kishi

  DOI：10.1021/ol9902374

  日期：1999.10.1

  [formula: see text] The revised structure of tolyporphin A O,O-diacetate (2b) was synthesized by assembling fragments 4, 5, and 12. The synthetic substance was found to be identical to the O,O-diacetate derived from natural tolyporphin A in every respect, thus establishing the relative and absolute configurations of this natural product.

  [公式：参见正文]通过组装片段4、5和12合成了甲苯酚AO，O-二乙酸酯（2b）的修正结构。发现该合成物质与天然甲苯酚中的O，O-二乙酸酯相同在各个方面都采用A，因此可以确定这种天然产品的相对和绝对构型。
• Total Synthesis of the Proposed Structure of (+)-Tolyporphin AO,O-Diacetate
  作者：Thomas G. Minehan、Yoshito Kishi

  DOI：10.1002/(sici)1521-3773(19990401)38:7<923::aid-anie923>3.0.co;2-7

  日期：1999.4.1

  Four monocyclic precursors were assembled in the total synthesis of the proposed structure 1-A of (+)-tolyporphin A O,O-diacetate (X=Ac). Comparison of the spectroscopic data demonstrated that synthetic tolyporphin O,O-diacetate did not match the O,O-diacetate prepared from natural (+)-tolyporphin A (X=H), calling for a structural revision of this class of natural products. On the basis of a series of NMR experiments including synthetic intermediates, the structure of tolyporphin A is concluded to be 1-B, in which the configurations of quaternary centers C7 and C17 are opposite to those in the originally proposed structure.
• Extension of the Eschenmoser sulfide contraction/iminoester cyclization method to the synthesis of tolyporphin chromophore
  作者：Thomas G. Minehan、Yoshito Kishi

  DOI：10.1016/s0040-4039(97)01601-8

  日期：1997.9

  Tolyporphin chromophore 2 has been synthesized by performing a double-retroaldol/oxidation sequence on an octahydroporphyrin precursor 28 prepared by using the Eschenmoser sulfide-contraction/iminoester-condensation method. (C) 1997 Elsevier Science Ltd.