5-hydroxypentyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate | 257629-47-3

• 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: 5-hydroxypentyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
• CAS: 257629-47-3
• 化学式: C₁₃H₂₅NO₄
• 分子量: 259.346
• InChiKey: GPIQUWXLOOLPSG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.13
• 重原子数：
  18.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  59.0
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  5-hydroxypentyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate 在 吡啶 、 4-二甲氨基吡啶 、 四溴化碳 、 trimethoxythioether 、 potassium tert-butylate 、 仲丁基锂 、 potassium carbonate 、 三苯基膦 、 鹰爪豆碱 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 27.25h， 生成 (-)-(1R,2S)-2-benzylcyclopentyl acetate
  参考文献：
  名称：

  (−)-Sparteine-Mediated Asymmetric Intramolecular Carbolithiation of Alkenes: Synthesis of Enantiopure Cyclopentanes with Three Consecutive Stereogenic Centers

  摘要：

  An asymmetric intramolecular carbolithiation reaction was developed by combining the (-)-sparteine-mediated enantiotopos-differentiating deprotonation and the anionic 5-exo-trig cyclization. Achiral 6-phenyl-hex-5-enyl carbamates were efficiently cyclized furnishing regio-, diastereo- (dr > 99:1),and enantioselectively (er >98:2) 1,2-trans-substituted cyclopentanes. The intermediate primary benzylic Lithium-carbanion pairs were - in spite of their configurative lability - diastereoselectively substituted by versatile electrophiles creating a third consecutive stereogenic center. Additionally, some 4-functionalized 6-phenylhex-5-enyl carbamates were also cyclized in high yield to provide enantiomericaliy pure cyclopentanes incorporating three adjacent stereogenic centers.

  DOI：

  10.1002/(sici)1522-2675(19991110)82:11<1860::aid-hlca1860>3.0.co;2-8
• 作为产物：
  描述：

  1,4-丁二醇 、 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carbonyl chloride 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以87%的产率得到5-hydroxypentyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
  参考文献：
  名称：

  （-）-斯巴汀碱介导的炔烃的立体选择性分子内碳氢化

  摘要：

  由4-取代的5-己炔基氨基甲酸酯的手性碱基s-丁基锂/（-）-天冬氨酸介导的不对称去质子化反应，可以合成对映体富集的碳负离子对，该对离子通过区域选择性的5- exo - dig环封闭，其中三键充当内部亲电体。高产率地形成具有完全立体选择性的官能化五元环。

  DOI：

  10.1016/s0040-4039(98)00085-9

文献信息

• (−)-Sparteine-Mediated Stereoselective Intramolecular Carbolithiation of 4-Substituted 5-Hexynyl Carbamates. Synthesis of Enantiopure 1,3-Difunctionalized Alkylidene Cyclopentanes
  作者：Martin Oestreich、Roland Fröhlich、Dieter Hoppe

  DOI：10.1021/jo991095u

  日期：1999.11.1

  The stereoselective carbolithiation of alkynes with external chiral induction has been achieved for the first time by fusing the concepts of the asymmetric deprotonation (A) with s-BuLi/(-)-sparteine (s-BuLi/1) and the intramolecular carbolithiation (B). Several 4-functionalized 5-hexynyl carbamates with different terminal substituents have been prepared and efficiently cyclized providing enantiopure highly substituted alkylidene cyclopentanes. The presence of a sterically demanding substituent in the propargylic position is the essential feature of these cyclizations in order to suppress the abstraction of the remaining propargylic proton. Furthermore, in dependence on the terminal substituent, the 6-phenyl-substituted precursors undergo an intramolecular carbolithiation whereas for the 6-trimethylsilyl-substituted alkynes a sub sequent migration of the O-carbamoyl group onto the vinylic carbanionic center follows.