(S)-4-Isopropyl-2-oxo-oxazolidine-3-carbaldehyde | 566174-28-5

• 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: (S)-4-Isopropyl-2-oxo-oxazolidine-3-carbaldehyde
• 英文别名: (4S)-2-oxo-4-propan-2-yl-1,3-oxazolidine-3-carbaldehyde
• CAS: 566174-28-5
• 化学式: C₇H₁₁NO₃
• 分子量: 157.169
• InChiKey: HHXJKPZZPJYCRV-ZCFIWIBFSA-N

物化性质

• 沸点：
  206.1±23.0 °C(Predicted)
• 密度：
  1.247±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (E,4S,3'RS)-3-(2',3'-diphenylbut-1'-enyl)-4-isopropyloxazolidin-2-one 在 氧气 、 亚甲兰 作用下， 以 二氯甲烷-D2 为溶剂， 反应 0.33h， 生成 (S)-1,2-二苯基丙酮 、 1,2-diphenylpropan-1-one 、 (S)-4-Isopropyl-2-oxo-oxazolidine-3-carbaldehyde
  参考文献：
  名称：

  单线态氧，臭氧和三唑啉二酮氧化手性恶唑烷酮官能化的氨基甲酸酯时观察到的立体选择性趋势的比较机理分析

  摘要：

  配备了恶唑烷酮手性助剂的E / Z氨基甲酸酯1在反应中的立体选择性已针对单线态氧（1 O 2），臭氧（O 3）和4-苯基-1,2,4-三唑啉进行了检测。 -3,5-二酮（PTAD）在各种溶剂中随温度的变化而变化。烯基官能度被1 O 2和O 3氧化裂解，释放出对映异构体富集的甲基脱氧安息香（MDB）产物。的程度（％ee），为以及所述感测（ř VS小号MDB形成中的立体选择性取决于氧化剂的电子性质。对于与1 O 2的反应，显示出基本上取决于溶剂和温度的高立体选择性，而基态反应物O 3和PTAD几乎不受溶剂和温度变化的影响。目前的比较分析清楚地证实了我们对进攻的1 O 2的立体选择性振动淬灭的假设，而O 3和PTAD仅受到空间位点的影响。电子激发1 O 2是体现在手性enecarbamates，所有这三个立体化学相关的结构特性敏感即- [R /小号配置在C 4的恶唑烷酮手性辅助剂，所述的位置Ž /

  DOI：

  10.1016/j.tet.2006.07.105

文献信息

• Stereoselective Photooxidation of Enecarbamates:  Reactivity of Ozone vs Singlet Oxygen
  作者：J. Sivaguru、Hideaki Saito、Thomas Poon、Toma Omonuwa、Roberto Franz、Steffen Jockusch、Catherine Hooper、Yoshihisa Inoue、Waldemar Adam、Nicholas J. Turro

  DOI：10.1021/ol0502230

  日期：2005.5.1

  Oxazolidinone-functionalized enecarbamates show contrasting behavior upon oxidation by singlet oxygen and by ozone. The observed stereoselectivity difference indicates that the oxidation with ozone is subject to classic steric effects, whereas the very high selectivity in the photooxidation with singlet oxygen is derived from vibrational deactivation.

  [反应：请参见文字]。恶唑烷酮官能化的氨基甲酸酯在被单线态氧和臭氧氧化时表现出相反的行为。观察到的立体选择性差异表明，臭氧的氧化具有经典的空间效应，而单线态氧的光氧化中的极高选择性则来自振动失活。
• A Supramolecular “Ship in Bottle” Strategy for Enantiomeric Selectivity in Geminate Radical Pair Recombination
  作者：Thomas Poon、Nicholas J. Turro、Jessica Chapman、P. Lakshminarasimhan、Xuegong Lei、Waldemar Adam、Sara G. Bosio

  DOI：10.1021/ol034362y

  日期：2003.6.1

  [reaction: see text] Reactions in which zeolites are modified with chiral inductors to serve as media for chiral induction are often limited by the propensity of both substrate and inductor to occupy the same supercage. Herein, we report a "ship in bottle" strategy utilizing the thermal decomposition of dioxetanes obtained from oxazolidinone-substituted enecarbamates for the enantioselective generation

  [反应：见正文]用手性感应剂改性沸石以用作手性感应介质的反应通常受基质和感应剂占据同一超笼的倾向限制。本文中，我们报告了一种“瓶装运输”策略，该策略利用了从恶唑烷酮取代的烯甲氨基甲酸酯获得的二氧环乙烷的热分解，用于对映选择性地生成甲基脱氧安息香（MDB）。超分子双峰分子对的光激发导致MDB的相反对映异构体富集。
• Stereocontrol within Confined Spaces:  Enantioselective Photooxidation of Enecarbamates Inside Zeolite Supercages
  作者：J. Sivaguru、Thomas Poon、Roberto Franz、Steffen Jockusch、Waldemar Adam、Nicholas J. Turro

  DOI：10.1021/ja046115a

  日期：2004.9.1

  Dye-exchanged Y zeolite is shown to be an effective medium to control the stereoselectivity in the photooxygenation of chiral oxazolidinone-functionalized Z/E-1 enecarbamates. An enantioselectivity (ee) as high as 80% was observed in the methyldesoxybenzoin (MDB) product, obtained in the methylene-blue-exchanged NaY zeolite at room temperature. The efficacy of the asymmetric induction in the MDB product depends on the Z/E geometry of the alkene, the Z-isomer being more effective than the corresponding E-isomer. The stereoselectivity is rationalized in terms of conformational effects through cationic interactions between the zeolite and the substrate.
• Stereochemical Features of the Physical and Chemical Interactions of Singlet Oxygen with Enecarbamates
  作者：Thomas Poon、Nicholas J. Turro、Jessica Chapman、P. Lakshminarasimhan、Xuegong Lei、Steffen Jockusch、Roberto Franz、Ilyas Washington、Waldemar Adam、Sara G. Bosio

  DOI：10.1021/ol035856y

  日期：2003.12.1

  [GRAPHICS]Oxazolidinone-substituted enecarbamates represent a mechanistically rich system for the study of stereoelectronic, steric, and conformational effects on stereoselectivity and mode selectivity in O-1(2) [2 + 2] and ene reactions. Photooxygenation of these enecarbamates with O-1(2) leads to diastereomerically pure dioxetanes that decompose to yield an oxazolidinone carbaldehyde and one of the two enantiomers of methyldesoxybenzoin in enantiomeric excess. Stereoselectivity originates at the allylic stereocenter, a result supported by quenching studies, computational analysis, and deuterium solvent isotope effects.
• 10.1562/2005-06-15-ra-573
  作者：Sivaguru、Saito, Hideaki、Solomon, Marissa R.、Kaanumalle, Lakshmi S.、Poon, Thomas、Jockusch, Steffen、Adam, Waldemar、Ramamurthy、Inoue, Yoshihisa、Turro, Nicholas J.

  DOI：10.1562/2005-06-15-ra-573

  日期：——