(E,4S,3'RS)-3-(2',3'-diphenylbut-1'-enyl)-4-isopropyloxazolidin-2-one | 763141-40-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (E,4S,3'RS)-3-(2',3'-diphenylbut-1'-enyl)-4-isopropyloxazolidin-2-one
• 英文别名: (4S)-3-[(E)-2,3-diphenylbut-1-enyl]-4-propan-2-yl-1,3-oxazolidin-2-one
• CAS: 763141-40-8
• 化学式: C₂₂H₂₅NO₂
• 分子量: 335.446
• InChiKey: ZLJBSEQHHRSVAH-KHIUIIDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  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 氘代氯仿 为溶剂， 生成 (S)-1,2-二苯基丙酮 、 1,2-diphenylpropan-1-one
  参考文献：
  名称：

  氨基甲酸酯的立体选择性光氧化：臭氧与单线态氧的反应性。

  摘要：

  [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。

  DOI：

  10.1021/ol0502230
• 作为产物：
  描述：

  (S)-3-((Z)-2,3-Diphenyl-but-1-enyl)-4-isopropyl-oxazolidin-2-one 以 二氯甲烷 为溶剂， 反应 0.33h， 生成 (E,4S,3'RS)-3-(2',3'-diphenylbut-1'-enyl)-4-isopropyloxazolidin-2-one
  参考文献：
  名称：

  10.1562/2005-06-15-ra-573

  摘要：

  DOI：

  10.1562/2005-06-15-ra-573

文献信息

• A comparative mechanistic analysis of the stereoselectivity trends observed in the oxidation of chiral oxazolidinone-functionalized enecarbamates by singlet oxygen, ozone, and triazolinedione
  作者：J. Sivaguru、Thomas Poon、Catherine Hooper、Hideaki Saito、Marissa R. Solomon、Steffen Jockusch、Waldemar Adam、Yoshihisa Inoue、Nicholas J. Turro

  DOI：10.1016/j.tet.2006.07.105

  日期：2006.11

  stereoselectivity, substantially dependent on solvent and temperature, is displayed for the reactions with 1O2, whereas the ground-state reactants O3 and PTAD are rather unaffected by solvent and temperature variations. The present comparative analysis clearly substantiates our hypothesis of stereoselective vibrational quenching of the attacking 1O2, whereas O3 and PTAD are only subject to steric impositions. The

  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 /
• 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。
• 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.
• Temperature and Solvent Control of the Stereoselectivity in the Reactions of Singlet Oxygen with Oxazolidinone-Substituted Enecarbamates
  作者：Thomas Poon、J. Sivaguru、Roberto Franz、Steffen Jockusch、Claudia Martinez、Ilyas Washington、Waldemar Adam、Yoshihisa Inoue、Nicholas J. Turro

  DOI：10.1021/ja048438c

  日期：2004.9.1

  Oxazolidinone-functionalized enecarbamates react stereoselectively with singlet oxygen to give methyldesoxybenzoin (MDB) in moderate to high enantiomeric excess. The stereochemical outcome depends on the E/Z substrate geometry, temperature, and solvent variables. The analysis of the differential activation parameters suggests a large contribution from the entropy term in determining the enantioselectivity. We demonstrate the utility of the temperature and solvent variables in determining the degree of the photochemical kinetic resolution of the enecarbamates; for example, in the photooxygenation at -70 degrees C in methanol, MDB may be obtained in methanol.
• Conformationally controlled (entropy effects), stereoselective vibrational quenching of singlet oxygen in the oxidative cleavage of oxazolidinone-functionalized enecarbamates through solvent and temperature variations
  作者：J. Sivaguru、Marissa R. Solomon、Hideaki Saito、Thomas Poon、Steffen Jockusch、Waldemar Adam、Yoshihisa Inoue、Nicholas J. Turro

  DOI：10.1016/j.tet.2006.01.119

  日期：2006.7

  by appropriate solvent and temperature conditions. Highlighted is the finding that the formation of the preferred MDB enantiomer (R or S) depends for the E isomer on the chosen solvent and temperature, but not for the corresponding Z isomer. The activation parameters for the various solvents disclose that differential entropy effects (ΔΔS‡) dominate the conformationally more flexible E diastereomers

  配备恶唑烷酮手性助剂的E / Z氨基甲酸酯的光氧合（亚甲基蓝作为敏化剂）时，烯基官能团的氧化裂解会释放出对映异构体富集的甲基脱氧安息香（MDB）产物。MDB形成中立体选择性的程度（％ee）以及立体感（R vs S）取决于烯烃构型的选择。立体控制的功效可通过适当的溶剂和温度条件进行调整。突出的发现是，优选的MDB对映异构体（R或S）的形成取决于E异构体取决于所选的溶剂和温度，但不适用于相应的Z异构体。对于各种溶剂的激活参数公开了微分熵效应（ΔΔ小号‡）占主导地位的构象更灵活ë非对映体。作为此空前构象施加的立体化学行为的机械原理，我们提出了烯丙基氨基甲酸酯对进攻单线态氧的立体选择性振动猝灭与空间控制的双键立体选择性氧化裂解的竞争作用。