(S)-4-phenyl-3-vinyloxazolidin-2-one | 128900-61-8

• 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-phenyl-3-vinyloxazolidin-2-one
• 英文别名: 3-vinyl-(S)-4-phenyl-2-oxazolidinone；(4S)-3-ethenyl-4-phenyl-1,3-oxazolidin-2-one
• CAS: 128900-61-8
• 化学式: C₁₁H₁₁NO₂
• 分子量: 189.214
• InChiKey: SKPGTFFDNHRLGI-SNVBAGLBSA-N

物化性质

• 沸点：
  278.8±43.0 °C(Predicted)
• 密度：
  1.241±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 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：

  (S)-4-phenyl-3-vinyloxazolidin-2-one 在 potassium pentacarbonylchromate 、 碳酸氢钠 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 水 、 苯 为溶剂， 反应 99.5h， 生成 (4S)-3-[(4S,5S)-1,10-dioxaspiro[4.5]dec-2-en-4-yl]-4-phenyl-1,3-oxazolidin-2-one
  参考文献：
  名称：

  光学合成的螺旋缩酮的合成和反应性，是通过铬碳烯络合物衍生的环丁酮的环扩环实现的。

  摘要：

  环状铬烷氧基卡宾配合物与旋光烯-氨基甲酸酯的光解得到螺合的旋光环丁酮。Baeyer-Villiger扩环，然后进一步官能化，得到旋光螺帽。这些螺旋稠合的环丁酮在乙酸或苯硫酚存在下的光化学环扩环得到2-乙酰氧基-或2-（硫代苯氧基）-4-螺合的四氢呋喃。消除噻吩氧基基团得到3，4-二氢呋喃，其经过Heck芳基化和与铬卡宾络合物的光化学环加成反应得到环丁酮。

  DOI：

  10.1021/jo971665v
• 作为产物：
  描述：

  L-苯甘氨酸 在 sodium tetrahydroborate 、 三氟化硼乙醚 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 生成 (S)-4-phenyl-3-vinyloxazolidin-2-one
  参考文献：
  名称：

  Synthesis of optically active butenolides via chromium alkoxycarbene complexes: total synthesis of (+)-tetrahydrocerulenin and two butenolides from the marine sponge Plakortis lita

  摘要：

  Optically active butenolides were synthesized from the corresponding cyclobutanones, derived from the photolysis of chromium alkoxycarbene complexes and optically active ene-carbamates. The cyclobutanones were oxidized (Baeyer-Villiger) to the corresponding lactones, and subsequent base-induced elimination of the beta-oxazolidinone ring provided optically active butenolides efficiently. The butenolides were utilized in the syntheses of (+)-tetrahydrocerulenin and two marine natural products.

  DOI：

  10.1021/jo00076a044

文献信息

• Synthesis of N-Vinyloxazolidinones and Morpholines from Amino Alcohols and Vinylsulfonium Salts: Analysis of the Outcome's Dependence on the N-Protecting Group by Nanospray Mass Spectrometry
  作者：Muhammad Yar、Sven P. Fritz、Paul J. Gates、Eoghan M. McGarrigle、Varinder K. Aggarwal

  DOI：10.1002/ejoc.201101272

  日期：2012.1

  in annulation reactions with diphenylvinylsulfonium triflate has been investigated. Although tosyl and sulfinamide groups give morpholines in high yields, the use of N-Cbz leads to a high-yielding synthesis of N-vinyloxazolidinones. The reactions were monitored by nanospray MS/MS, which revealed why reactions are successful and the fate of reactive intermediates in the unsuccessful reactions.

  已经研究了在与二苯基乙烯基锍三氟甲磺酸盐的成环反应中 N-保护基团的性质对 1,2-氨基醇的影响。尽管甲苯磺酰基和亚磺酰胺基团以高产率提供吗啉，但使用 N-Cbz 导致 N-乙烯基恶唑烷酮的高产率合成。通过纳米喷雾 MS/MS 监测反应，这揭示了反应成功的原因以及不成功反应中反应中间体的命运。
• Synthesis of 4-Alkyl-4-alkoxybutenolides Having Unsaturated Side Chains via Chromium Carbene Complex Photochemistry:  (+)-Cerulenin
  作者：Tracey E. Kedar、Michael W. Miller、Louis S. Hegedus

  DOI：10.1021/jo960664k

  日期：1996.1.1

  photochemical reaction between optically active ene carbamates and chromium alkoxycarbene complexes containing unsaturated aliphatic side chains was further developed. Although remote olefinic groups, including conjugated dienes, were tolerated, a homoallylic side chain underwent intramolecular reaction to give a strained cyclobutanone. (+)-Cerulenin was synthesized utilizing the photochemical reaction of an

  进一步发展了光学活性烯氨基甲酸酯与含不饱和脂族侧链的铬烷氧基卡宾配合物之间的光化学反应。尽管容忍了包括共轭二烯在内的远端烯烃基团，但均烯丙基侧链发生了分子内反应，从而得到了应变的环丁酮。利用炔基卡宾配合物与旋光性氨基甲酸酯的光化学反应和乙烯基溴的双（β-巴豆基）卤化镍烷基化反应为关键步骤合成了（+）-Cerulenin。
• De Novo Synthesis of 4‘-Ethoxy Nucleoside Analogues
  作者：Louis S. Hegedus、Lisa Geisler、Andrew G. Riches、Sarri S. Salman、Gisela Umbricht

  DOI：10.1021/jo020151f

  日期：2002.11.1

  Butenolides 5a and 13 were used as optically active templates in the de novo synthesis of 4'-disubstituted nucleoside analogues. The butenolides were reduced and acylated in situ to give acetates 10 and 14. Vorbrüggen coupling gave the protected nucleoside analogues 11 and 15. Reduction of 11 gave 4'-ethoxy-2',3'-dideoxythymidine (6) and deprotection of 15 gave 4'-ethoxy-2',3'-dideoxydidehydrothymidine

  丁烯内酯5a和13用作4'-二取代核苷类似物的从头合成中的旋光模板。还原丁烯内酯并原位酰化得到乙酸酯10和14。Vorbrüggen偶联得到受保护的核苷类似物11和15。还原11得到4′-乙氧基-2′，3′-二脱氧胸苷（6）和15的脱保护基得到4′-乙氧基-2′，3′-二脱氧二氢胸苷（7）。发生了多种丁烯内酯的顺二羟基化反应，主要产物由β面的氧化形成。
• Effect of β-Substituents on the Regioselectivity of the Diazomethane Ring Expansion of α-Methyl-α-methoxycyclobutanones to Cyclopentanones
  作者：Lisa M. Reeder、Louis S. Hegedus

  DOI：10.1021/jo990226o

  日期：1999.4.1

  The ring expansion of 22 differently beta-substituted alpha-methyl-alpha-methoxycyclobutanones by diazomethane was studied. Migration of the less-substituted alpha-carbon was favored with the single exception of a very sterically hindered beta-benzyloxy beta-substituent.

  研究了重氮甲烷对22种不同的β-取代的α-甲基-α-甲氧基环丁酮的扩环作用。除了非常受空间阻碍的β-苄氧基β-取代基以外，较少取代的α-碳的迁移是有利的。
• Synthesis of optically active ene carbamates from chromium carbene complexes: use in palladium(II)-assisted synthesis of relays to (+)-thienamycin
  作者：John Montgomery、Gary M. Wieber、Louis S. Hegedus

  DOI：10.1021/ja00173a012

  日期：1990.8

  prepare optically active chromium carbene complexes containing the oxazolidinone moiety led instead to an efficient and general synthesis of optically active ene carbamates. One of these has been subjected to palladium(II)-assisted carboacylation, and complete control of stereochemistry was observed. This compound was converted to a key relay to (+)-thienamycin in good chemical and very high optical yield

  尝试制备含有恶唑烷酮部分的光学活性铬卡宾配合物，反而导致了光学活性烯氨基甲酸酯的有效和通用合成。其中之一已进行钯 (II) 辅助的碳酰化，并观察到立体化学的完全控制。该化合物以良好的化学和非常高的光学产率转化为 (+)-硫霉素的关键中继